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2018 Results for Per- and Polyfluoroalkyl Substances (PFAS) Analyses Performed by United States
Environmental Protection Agency’s Office of Research and Development for Samples Collected in Southern
New Hampshire
April 2019
2018 Results for Per- and Polyfluoroalkyl Substances (PFAS) Analyses Performed by United States
Environmental Protection Agency’s Office of Research and Development for Samples Collected in Southern
New Hampshire
2018 Summary Report
Prepared by
Catherine Beahm, SIP Planning Administrator Air Resources Division
And
Jeffrey Marts, Project Manager
Waste Management Division
Robert Scott, Commissioner Clark Freise, Assistant Commissioner
Craig A Wright, Director, Air Resources Division Michael Wimsatt, Director, Waste Management Division
Thomas O’Donovan, Director, Water Division
April, 2019
New Hampshire Department of Environmental Services
PO Box 95, Concord, NH 03302-0095 des.nh.gov | (603) 271-3503
Acknowledgements NHDES would like to thank Meghan Cassidy, EPA Region 1, for facilitating the partnership with United States Environmental Protection Agency’s Office of Research and Development (EPA ORD). Special thanks go to Jennifer Orme-Zavaleta, PhD, the previous Director and Timothy H. Watkins, the current Director of the National Exposure Research Laboratory who granted EPA ORD assistance following requests by NHDES. NHDES is grateful for the opportunity to work closely with the many talented EPA ORD scientists and staff. NHDES would like to acknowledge the many property owners who provided access for sample collection. Without their cooperation, this important project would not be possible.
Table of Contents 1. Introduction 2. Project Overview 3. Sample Collection 4. EPA ORD Reports Table 1 Table 2 Figure 1 Appendices A-1: NHDES Letter – New Hampshire Department of Environmental Services Request for
Assistance Assessing Poly- and Perfluoroalkyl Substances dated June 22, 2017 A-2: Work Plan #1 – Southern New Hampshire Sample Collection Plan for Non-Targeted Per-
and Poly-fluorinated Compounds Analyses dated August 30, 2017 A-3: NHDES Letter – New Hampshire Department of Environmental Services Request for
Additional Assistance Assessing Poly- and Perfluoroalkyl Substances dated October 27, 2017
A-4: Work Plan #2 – Saint-Gobain Performance Plastics Air Sample Collection Plan for Non-Targeted Per- and Polyfluoroalkyl Substances Analysis dated April 18, 2018
A-5: Stack Test Plan Saint Gobain Performance Plastics Corporation Merrimack, New Hampshire dated April 11, 2018
A-6: ORD Report #1 dated April 4, 2018 A-7: ORD Report #2 dated July 24, 2018 A-8: ORD Report #3 dated October 4, 2018 A-9: ORD Report #4 dated October 4, 2018
1. Introduction In 2017, the New Hampshire Department of Environmental Services (NHDES) requested assistance from the United States Environmental Protection Agency’s Office of Research and Development (EPA ORD) to conduct analyses of various samples for the potential existence of per- and polyfluoroalkyl substances (PFAS) (Appendix A-1 and A-3) . The type of samples identified by NHDES for analysis included industrial coating formulations, air emissions, groundwater, surface water, soil and leachate. Specifically, NHDES was interested in samples taken near sites where there was the potential for air emissions associated with processes that historically and currently use PFAS-containing raw materials. The release of PFAS compounds into the environment from these sites has contaminated soil and water, including groundwater used as drinking water for tens of thousands of people in the state. Assistance from EPA ORD was requested in order to address several technical barriers that included: 1) commercial laboratory analytical limitations for handling more complex sample matrices; 2) unknown nature of the compounds because they are either proprietary, manufacturing byproducts contained in raw materials, or degradation compounds; and 3) lack of expertise and experience associated with advanced fluorochemistry and fate and transport properties of this class of compounds. Specifically, EPA ORD has unique capabilities to conduct “non-targeted” screening, whereby a search is conducted of a broader spectrum of PFAS that may be present in a sample, including both known and unknown compounds; this type of analysis is not available through a commercial laboratory. NHDES has several objectives for this on-going partnership with EPA to evaluate PFAS in samples collected from New Hampshire:
1) Understand the multimedia environmental distribution of fluorinated compounds originating from PFAS emissions to air;
2) Differentiate sources of contamination when and where there is the potential for multiple PFAS sources by identifying a signature distribution of compounds for different sources of PFAS;
3) Assess if conditions warrant the installation of treatment systems for air emissions to proactively prevent the contamination of the environment and drinking water with newer alternative chemicals or precursor compounds;
4) Ensure any potential air pollution control equipment systems that may be required to be installed are designed to remove not only perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), but a broader array of PFAS compounds and associated break-down products, some which could be precursors to the formation of PFOA and PFOS. This information is critical for ensuring any air pollution control equipment is properly designed for potential PFAS emissions and that remediation
systems removing PFOA and PFOS do not unknowingly redistribute other PFAS contaminants;
5) Ensure drinking water treatment systems and remediation systems being designed to remove PFOA and PFOS are also able to remove other PFAS compounds and associated break-down products, some which could be precursors to the formation of PFOA and PFOS. This information is critical for ensuring drinking water is appropriately treated and that remediation systems removing PFOA and PFOS do not unknowingly redistribute other PFAS contaminants; and
6) Prioritize which contaminant(s) need a risk assessment based on what is actually being
measured in the environment, including drinking water. In 2018, the EPA produced four reports that document the results of analyses conducted to date as part of the ongoing partnership with NHDES. These reports are the first in what is expected to be a series of reporting by the EPA on the results of New Hampshire sample analyses. In many respects, the analytical work conducted by EPA ORD is at the forefront of the emerging science of PFAS. NHDES is pleased to be working closely with EPA ORD on this contamination issue that is of such vital concern to the citizens of New Hampshire. The EPA data reports are intended to provide a simple representation and summary of the analysis results. Therefore, the description of methods and quality assurance are brief and high-level. Additional reports and/or publications are being developed that will include a more detailed description of methods, quality assurance analyses, and statistical/geospatial interpretation of the data. As study partners/collaborators, it is anticipated that NHDES and EPA Region 1 scientists will assist in these additional reports and publications.
2. Project Overview NHDES and EPA jointly developed two work plans for the sampling and analysis related to the investigation into releases of PFAS compounds to the air from industrial facilities in NH. Those plans are: Work Plan #1: Southern New Hampshire Sample Collection Plan for Non-Targeted Per- and Poly-fluorinated Compounds Analyses dated August 30, 2017. (Appendix A-2) This plan guided the collection and analyses of samples from several different environmental media including groundwater, surface water, and soil as well as industrial samples of raw materials used in dispersions at two facilities and solid material (referred to as char) that accumulates inside the air emission stacks. Work Plan #2: Saint-Gobain Performance Plastics Air Sample Collection Plan for Non-Targeted Per- and Polyfluoroalkyl Substances Analysis dated April 18, 2018. (Appendix A-4)
This plan guided the collection and analyses of samples from process feedstocks, pilot-scale air pollution control equipment, and air emissions from three towers during a multiday stack testing event in April and May 2018 at Saint-Gobain Performance Plastics (SGPP).
3. Sample Collection 3.1 Work Plan #1: NHDES staff collected samples of groundwater, surface water, soil, raw materials used in dispersions, and char in general accordance with Work Plan #1, as described in the sections below. Samples were then submitted to EPA ORD for analysis. For logistical reasons, some of the samples proposed in the Work Plan were not able to be collected (e.g., dust was not able to be sampled due to lack of sufficient sample volume).
3.1.1 Groundwater A total of 20 groundwater samples (including three duplicate samples) were collected and submitted to EPA ORD (Figure 1, Table 1). Groundwater sources sampled for this study included monitoring wells and private wells no longer used for drinking. Wells were selected for inclusion in this study based on results of prior PFAS analyses so that a range of PFAS concentrations could be evaluated, including highly contaminated monitoring wells close to the facility, wells with PFOA concentrations between 0.05 and 0.10 ng/L, and wells with PFOA concentrations exceeding 0.20 ng/L.
3.1.2 Surface Water Surface water samples (including one duplicate sample) were collected from five different locations and submitted to EPA ORD (Figure 1, Table 1). Samples were collected from the Merrimack River (EPAORD 002 and EPAORD 003) and Dumpling Brook (EPAORD 001, EPAORD 003, and duplicate sample EPAORD 004). Discharge from the stormwater system that drains the SGPP facility was sampled at the Outfall (EPAORD 006) during dry conditions when the water discharging from the system is likely due to groundwater infiltration.
3.1.3 Soil Three soil samples were collected from different depths at a single boring location near the SGPP facility (Figure 1, Table 1). NHDES staff advanced the boring to a total depth of six feet below the ground surface using a stainless steel hand auger. The three intervals sampled for this study included the surface soil (EPAORDS1 or NHEPAORD-S1), an interval two to four feet below ground (EPAORDS2 or NHEPAORD-S2), and the interval from four to six feet below ground (EPAORDS3 or NHEPAORD-S3).
3.1.4 Char Material from Tower Stacks NHDES staff collected three samples of solid material (char) that coats the interior of the stacks of the textile coating towers. The three towers were chosen because they have the potential to represent three different operational situations (Figure 1, Table 1):
1) The MA Tower has been in operation since 1994. The ductwork was replaced and the oven and ancillary process components were cleaned in 2016. Therefore, the solid material (Sample ID: MA Tower Char or NHCharMA) that was collected from this stack will most likely represent “new” dispersions used since 2016.
2) The MS Tower has been in operation since 2002. The solid material (Sample ID: MS Tower Char or NHCharMS) that was collected from this stack may potentially contain residue components from pre-2006 PFOA-based dispersions AND “new” dispersions that have been used since 2006.
3) The QX Tower has been in operation since 1989. According to historical stack testing
results, the QX Tower receives the highest load of emissions, and solid material (Sample ID: QX Tower Char or NHCharQX) that was collected from this stack would likely be associated with emissions that occurred while PFOA-based dispersions were in use and emissions that occurred after the use of PFOA had been phased out.
3.1.5 Raw Materials used in Dispersions
NHDES staff collected a total of thirteen raw material samples (Sample IDs: 1 – 13) from the two textile coating facilities. According to company representatives and records, these samples represent all of the raw materials containing fluorinated compounds currently stored or in use at the two facilities. 3.2 Work Plan #2: In addition to and in conjunction with Work Plan #2, NHDES requested that SGPP conduct air emission stack testing of three towers in order to collect the samples for analysis by EPA ORD. The stack tests were conducted April 26 – May 2, 2018 by SGPP and their consultants while NHDES personnel were present to observe the process operations, sampling, and stack testing methodology and also to facilitate transmission of samples to EPA ORD. The stack tests were conducted in accordance with the approved stack test plan submitted by SGPP and dated April 11, 2018. (Appendix A-5). Stack tests were conducted on the MA, MS and QX Towers. Samples were taken from the QX Tower at the inlet and outlet of a pilot-scale control device to evaluate its effectiveness at removal of PFAS compounds. Table 2 is a summary of all of the samples submitted to EPA ORD collected as part of Work Plan #2.
3.2.1 Air Emission Samples During each of the stack tests, a total of three runs were completed. During each run, a sample train comprised of seven segments was deployed. In total, 84 air emission samples were collected. These samples were taken by stack testing personnel and sent directly to EPA ORD for analysis. (Sample IDs: 500 – 520, 600 – 620, 700 – 720, 800 – 820)
3.2.2 SUMMA Canister Samples There were 18 SUMMA canister samples collected including two background samples, four ambient samples and 12 stack test runs. These samples were collected by NHDES personnel and sent directly to EPA ORD for analysis. (Sample IDs: 2 backgrounds, 709, 721, 176, A378, 321, 2045, 793, 005, 755, 751, 262, RK9, 068, 700, 744, 794)
3.2.3 Dip Tank Coatings Eleven total samples of actual coating utilized during each stack test were taken by stack testing personnel from the dip tank(s) for each tower and sent directly to EPA ORD for analysis. (Sample IDs: 521, 522, 523, 621, 622, 623, 721, 722, 725, 726, 729)
3.2.4 Char Material from Tower Stacks NHDES staff collected three samples of solid material (char) that coats the interior of the stacks of the three textile coating towers that were stack tested. (Sample IDs: MA, MS QX)
3.2.5 Process Water from Pilot-Scale Air Pollution Control Equipment Four samples of the process water that was used in the pilot scale air pollution control device were sampled by stack testing personnel and sent directly to EPA ORD for analysis. (Sample IDs: 733, 734, 735, 736)
4 EPA ORD Reports EPA ORD submitted four reports to NHDES in 2018 that convey results of analyses performed on the various samples from New Hampshire (Table 1 and Table 2). These reports represent the first in a series of data that will be presented to NHDES by EPA ORD; additional reports will be provided as EPA ORD finishes their analyses. Each report is included in its entirety in Appendices A-6 through A-9. The exhibit below summarizes the types of results provided in each report.
Exhibit 1 Report Number Date Sample Media Type of Analyses
ORD Report #1 April 4, 2018 Char and Soil Targeted PFCAs
ORD Report #2 July 24, 2018 Char and Soil Non-Targeted PFAS
ORD Report #3 October 4, 2018 Groundwater and Surface Water
Targeted PFAS
ORD Report #4 October 4, 2018 Stack Emissions SUMMA Canister
Samples Only
Non-Targeted PFAS and Volatile Organic
Hazardous Air Pollutants
4.1 ORD Report #1 ORD Report #1 contains the results of targeted perfluorocarboxylate1 (PFCA) concentrations for the two types of solid-matrix samples analyzed at the EPA ORD laboratory located in Athens, Georgia (Appendix A-6). Three samples each of char and soil were analyzed for thirteen PFCAs using liquid chromatography / mass spectrometry. Internal standards of each compound were used to quantify the laboratory results in terms of micrograms per gram (µg/g or parts per million (ppm)) for char and picograms per gram (pg/g or parts per trillion (ppt)) for soil. Key results of the report include:
Overall PFCA concentrations were greater in the char samples (reported in ppm) compared to the soil samples (reported in ppt).
Chain lengths of the PFCAs detected in char ranged from four carbons (C4) to 18 carbons (C18); whereas, the longest chain PFCA detected in soil was C11.
PFOA was the PFCA with the highest concentration in each of the six samples.
PFCA concentrations generally decreased with depth in the three samples from the soil boring.
4.2 ORD Report #2 ORD Report #2 contains the results of non-targeted PFAS concentrations for the two types of solid-matrix samples analyzed at the EPA ORD laboratory located in Athens, Georgia (Appendix A-7). The same samples of char and soil described in ORD Report #1 were analyzed for non-targeted PFAS using liquid chromatography / mass spectrometry. Known standards are not available for the analysis of the non-targeted compounds, therefore, there is more uncertainty in terms of identification of the compounds and estimation of concentrations. The results reported in units of µg/g for char and pg/g for soil, are considered to be estimated values. In other words, the results are “semi-quantitative, likely within an order of magnitude of the actual value” and have a greater level of uncertainty relative to results of analyses performed with known standards. Key results of the report include:
1 Perfluorocarboxylates are reported as perfluorocarboxylic acids.
Two types of PFAS were detected that have not been previously identified in environmental samples and include a polyfluoroalkyl carboxylic acid series and a polyfluorinated sulfonic acid (PFSA) series, each of which has a hydrogen atom substituted for a fluorine atom. The hydrogenated PFCA and PFSA series are referred to as HPFCA and HPFSA, respectively, in Report #2. Actual concentration values for HPFSA were not presented because they occurred at lower concentrations relative to HPFCA.
The number of carbon atoms in the HPFCAs detected in the samples ranged from C6 to C20 and from C4 to C18 for the HPFSAs.
Similar to PFCA results in Report #1, HPFCA concentrations were orders of magnitude greater in the char samples (reported in ppm) compared to the soil samples (reported in ppt).
HPFSA concentrations were greater than HPFCA by a factor of 10 and 1.2 for C6 and C8, respectively in the char samples. For the other carbon chain lengths, HPFCA was present at greater concentrations than HPFSA.
The surface soil sample (EPAORDS1 or NHEPAORD-S1) contained the greatest concentrations of HPFCA compared to deeper soil samples.
4.3 ORD Report #3 ORD Report #3 contains the results of targeted PFAS concentrations for groundwater and surface water samples analyzed at the EPA ORD laboratory located in Research Triangle Park, North Carolina (Appendix A-8). Twenty-five aqueous samples were analyzed for 11 PFAS using liquid chromatography / mass spectrometry. Standards of each compound were used to quantify the laboratory results in terms of nanograms per liter (ng/L). Key results of the report include:
PFOA was detected in 22 of 25 samples. In all samples where it was detected, PFOA had the greatest concentration of all of the other PFAS detected.
PFOS was not detected in any of the groundwater samples; however, it was detected in four of the five surface water samples and the sample from the stormwater outfall.
Perfluoro(2-methyl-3-oxahexanoic) acid, also known as GenX, a compound that is associated with a newer generation of PFAS that replaced PFOA, was detected in one groundwater sample from a domestic well (EPAORD 016) above the limit of quantification (LOQ) at a concentration of 35.4 ng/L. To NHDES’ knowledge, this represents the first detection of GenX in groundwater from a domestic well out of hundreds of samples from other domestic wells that have been tested for this compound by commercial laboratories. In consultation with EPA ORD staff, it is suggested that this sample be reanalyzed for conformational analysis of this unique finding and rule out laboratory contamination.
4.4 ORD Report #4 ORD Report #4 contains the results of non-targeted PFAS and volatile organic hazardous air pollutants (HAPs) analyses for the gases collected in SUMMA canisters during the stack test in April and May, 2018. Analyses were conducted at the EPA ORD laboratory located in Research Triangle Park, North Carolina (Appendix A-9). Due to this being the first time SUMMA canister sampling for PFAS compounds has been performed on stack emissions, the high resolution chemical ionization mass spectrometry (CIMS) analyses for the non-targeted PFAS are limited to tentative identifications, rather than quantification. The more conventional TO-15 analysis2 using unit mass resolution (low resolution) gas chromatography-mass spectrometry (GC-MS) can be understood as a targeted analysis of gas phase volatile organic hazardous air pollutants (HAPs). Key results of the report include:
The CIMS-based non-targeted analysis tentatively identified twelve (12) PFAS compounds in the SUMMA canisters.
The GC-MS targeted selective ion monitoring (SIM) analysis of SUMMA canisters identified 27, 42 and 38 non-PFAS compounds in the samples from the MS, MA and QX towers, respectively.
Up to 118 gas phase compounds were observed across all nine samples using the TO-15 (plus photochemical assessment monitoring station compounds) method.
Across all nine SUMMA canisters representing non-controlled stack emissions, the following compounds were observed in all canisters: propylene, propane, chloromethane, isobutene, 1-butene, ethanol, acrolein, acetone, iso-pentane, isopropyl alcohol, 1-pentene, isoprene, vinyl acetate, 2-butanone, 1-hexene, tetrahydrofuran, 2,4-dimethylpentane, benzene, 4-methyl-2-pentanone, toluene, and dodecane.
2 TO-15 is an EPA approved method for determination of volatile organic compounds (VOCs) in air collected in
specially prepared SUMMA canisters and analyzed by gas chromatography/mass spectrometry (GC/MS). http://www.caslab.com/EPA-Methods/PDF/to-15r.pdf
Sample Material Sample Number Sample Collection Date Sample Location DescriptionEPA ORD
Report(s)Type of Analyses Reported
199712055MWGZ1 5/31/2018 Monitoring Well NR Pending199712055MWGZ1 (duplicate) 5/31/2018 Monitoring Well NR Pending
199712055MWGZ2 5/31/2018 Monitoring Well NR Pending199712055MWGZ3 5/31/2018 Monitoring Well NR Pending
EPAORD_007 8/30/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_008 8/25/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_009 8/24/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_010 8/31/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_011 8/24/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_012 8/25/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pending
EPAORD_013 (dup) 8/25/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_014 8/31/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_015 8/29/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_016 8/31/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_017 8/31/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_018 8/25/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_019 8/30/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_020 8/30/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pending
EPAORD_021 (dup) 8/30/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_022 9/8/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_023 9/8/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pendingEPAORD_024 9/5/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pending
EPAORD_901 9/8/2017 Private Well #3 Targeted PFAS; non-Targeted PFAS results pending
EPAORD_001 8/28/2017 Dumpling Brook, Upstream #3 Targeted PFASEPAORD_002 8/28/2017 Merrimack River, Downstream #3 Targeted PFASEPAORD_003 8/28/2017 Merrimack River, Upstream #3 Targeted PFASEPAORD_004 8/28/2017 Dumpling Brook, Downstream #3 Targeted PFAS
EPAORD_005 (duplicate) 8/28/2017 Dumpling Brook, Downstream #3 Targeted PFAS
EPAORD_006 8/28/2017 Stormwater Outfall #3 Targeted PFAS
EPAORDS1 9/1/2017 Soil Boring (0") #1 & #2 Targeted PFCAs; Non-Targeted PFASEPAORDS2 9/1/2017 Soil Boring (2-4') #1 & #2 Targeted PFCAs; Non-Targeted PFAS
EPAORDS3 9/1/2017 Soil Boring (4-6') #1 & #2 Targeted PFCAs; Non-Targeted PFAS
MA Tower August, 2017 Interior of stack #1 & #2 Targeted PFCAs; Non-Targeted PFASMS Tower August, 2017 Interior of stack #1 & #2 Targeted PFCAs; Non-Targeted PFAS
QX Tower August, 2017 Interior of stack #1 & #2 Targeted PFCAs; Non-Targeted PFAS
1 August, 2017 Directly from container shipped by supplier NR Pending2 August, 2017 Directly from container shipped by supplier NR Pending3 August, 2017 Directly from container shipped by supplier NR Pending4 August, 2017 Directly from container shipped by supplier NR Pending5 August, 2017 Directly from container shipped by supplier NR Pending6 August, 2017 Directly from container shipped by supplier NR Pending7 August, 2017 Directly from container shipped by supplier NR Pending8 August, 2017 Directly from container shipped by supplier NR Pending9 August, 2017 Directly from container shipped by supplier NR Pending
10 August, 2017 Directly from container shipped by supplier NR Pending11 August, 2017 Directly from container shipped by supplier NR Pending12 August, 2017 Directly from container shipped by supplier NR Pending
13 August, 2017 Directly from container shipped by supplier NR Pending
PFCA Perfluorocarboxylates are reported as perfluorocarboxylic acids.PFAS Per- and Polyfluoroalkyl substances NR Not Reported
TABLE 1Summary of Samples Submitted to EPA ORD
WORK PLAN #1
Acronyms
Groundwater
Surface Water
Soil
Char Material from
Tower Stacks
Raw Materials Used
in Dispersions
for Poly- and Perfluoroalkyl Substances (PFAS) Analyses
Sample Material Sample Number Sample Collection Date Sample Location DescriptionEPA ORD
Report(s)Type of Analyses Reported
500-520 April 26 & 27, 2018 MA Tower NR Pending600-620 April 26 & 27, 2018 MS Tower NR Pending700-720 April 30 & May 1, 2018 QX Tower Inlet to Pilot-scale Control Device NR Pending
800-820 April 30 & May 1, 2018 QX Tower Outlet of Pilot-scale Control Device NR Pending
Background 1 System Blank #4 Non-Targeted PFAS; Volatile Organic HAPsRK9 5/1/2018 Ambient (inside facility) #4 Non-Targeted PFAS; Volatile Organic HAPs005 5/1/2018 Ambient (lower roof) #4 Non-Targeted PFAS; Volatile Organic HAPs794 4/27/2018 Ambient (upper roof) #4 Non-Targeted PFAS; Volatile Organic HAPs709 4/30/2018 Ambient (Field Blank) #4 Non-Targeted PFAS; Volatile Organic HAPs755 4/26/2018 MA Tower #4 Non-Targeted PFAS; Volatile Organic HAPs751 4/27/2018 MA Tower #4 Non-Targeted PFAS; Volatile Organic HAPs262 4/27/2018 MA Tower #4 Non-Targeted PFAS; Volatile Organic HAPs068 4/26/2018 MS Tower #4 Non-Targeted PFAS; Volatile Organic HAPs700 4/27/2018 MS Tower #4 Non-Targeted PFAS; Volatile Organic HAPs744 4/27/2018 MS Tower #4 Non-Targeted PFAS; Volatile Organic HAPs721 4/30/2018 QX Tower (inlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs176 5/1/2018 QX Tower (inlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs
A378 5/1/2018 QX Tower (inlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs321 4/30/2018 QX Tower (outlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs
2045 5/1/2018 QX Tower (outlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs793 5/1/2018 QX Tower (outlet to Pilot-scale Control Device) #4 Non-Targeted PFAS; Volatile Organic HAPs
Background 2 System Blank #4 Non-Targeted PFAS; Volatile Organic HAPs
521 4/26/2018 MA Tower NR Pending522 4/27/2018 MA Tower NR Pending523 4/27/2018 MA Tower NR Pending621 4/26/2018 MS Tower NR Pending622 4/27/2018 MS Tower NR Pending623 4/27/2018 MS Tower NR Pending721 4/30/2018 QX Tower Dip Pan 1 NR Pending722 4/30/2018 QX Tower Dip Pan 2-5 NR Pending725 5/1/2018 QX Tower Dip Pan 1 NR Pending726 5/1/2018 QX Tower Dip Pan 2-5 NR Pending
729 5/1/2018 QX Tower Dip Pan 1 NR Pending
MA Tower 5/2/2018 Interior of stack NR PendingMS Tower 5/2/2018 Interior of stack NR Pending
QX Tower 5/2/2018 Interior of stack NR Pending
733 5/1/2018 Supply Water NR Pending734 4/30/2018 Sump Water NR Pending735 5/1/2018 Sump Water NR Pending
736 5/1/2018 Sump Water NR Pending
PFCA Perfluorocarboxylates are reported as perfluorocarboxylic acids.PFAS Per- and Polyfluoroalkyl substances NR Not Reported
HAPs Hazardous Air Pollutants
SUMMA Canister
Samples
Process Water from
Pilot-Scale APCE
Char Material from
Tower Stacks
Dip Tank Coatings
Acronyms
Air Emission
Samples
TABLE 2Summary of Samples Submitted to EPA ORD
for Poly- and Perfluoroalkyl Substances (PFAS) AnalysesWORK PLAN #2
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EPAOR D 001
EPAOR D 004
EPAOR D 002
EPAOR D 003
EPAOR D 006
EPAOR D 010
EPAOR D 007
EPAOR D 023
EPAOR D 011
EPAOR D 009
EPAOR D 022EPAOR D 901
EPAOR D 020
EPAOR D 014
EPAOR D 018
EPAOR D 012 EPAOR D 015
EPAOR D 017
EPAOR D 016
EPAOR D 024
EPAOR D 008
EPAOR D 019
Merrimack
Bedford
Litchfield
Londonderry
Manchester
®
Figure 1 - EPA ORDSample Locations
0 0.5 10.25Miles
1 inch = 2,500 feet
MonitoringWell
SupplyWell
PFOA + PFOS (PPT)
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EPA ORD Sample Locations
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Map By: Jeffrey Marts and Samuel Fontaine
Document Path: S:\DES-COMMON\PFOAinvestigations\GISDatasets\EPAORD\ORD 2018 Figure 1.mxd
Tow n Boundary
Appendix A-1
NH DES Letter - New Hampshire Department of Environmental Services
Request for Assistance Assessing Poly- and Perfluoroalkyl Substances June 22, 2017
June 22, 2017
The State of New Hampshire
Department of Environmental Services
Clark B. Freise, Assistant Commissioner
Jennifer Orme-Zavaleta, PhD Director, National Exposure Research Laboratory USEPA Office of Research and Development 109 TW Alexander Dr MC 305-01 RTP, NC 27711
Subject: New Hampshire Department of Environmental Services Request for Assistance Assessing Poly- and Perfluoroalkyl Substances
Dear Dr. Orme-Zavaleta:
The New Hampshire Department of Environmental Services (NHDES} is requesting assistance for completing analyses of long and short-chain poly and perfluoroalkyl substances (PFAS) in industrial chemicals, groundwater, surface water, soil, sludge, air, process residuals and potentially food crops surrounding two sites where air emissions associated with processes that historically used PFAScontaining raw materials. These sites have historically released PFAS into the environment and have contaminated soil and water, including groundwater used as drinking water for tens of thousands of people in the state. NHDES is also concerned that ongoing air emissions of certain PFAS may be occurring with minimal air pollution controls being applied.
NH DES is currently using commercial laboratories to complete analyses that report results of 14 to 23 traditional PFAS compounds. NH DES has attempted to coordinate with a laboratory to analyze for a PFAS compound variant that was reported to have replaced PFOA at a facility that has ongoing air emissions containing PFAS. Despite analyzing over 1,000 samples from private and public drinking water wells in an area where groundwater has been contaminated with PFOA, this replacement compound has yet to be detected in water near this site. However, the replacement compound was detected in stack samples at the site.
Assistance from the United States Environmental Protection Agency (USEPA) is needed to test for environmental contaminants that are potentially being released to the air and impacting the environment. USEPA's assistance is needed to overcome technical barriers for completing this work to date including: 1) commercial laboratory analytical limitations for handling more complex sample matrices; 2) unknown nature of the compounds because they are proprietary, manufacturing byproducts or degradation compounds contained in raw materials; and 3) lack of expertise and experience associated with advanced fluorochemistry and fate and transport properties. USEPA could assist by analyzing samples using high resolution mass spectrometry with a comprehensive assessment of the spectral data using library searches.
www.des.nh.gov 29 Hazen Drive • PO Box 95 • Concord, NH 03302-0095
(603) 271-3503 • Fax: 271-2867 • TDD Access: Relay NH 1-800-735-2964
Jennifer Orme-Zavaleta, PhD USEPA Office of Research and Development June 22, 2017 Page 2 of 2
NH DES will utilize this information to: 1) understand the multimedia environmental distribution of fluorinated compounds generated when emitting PFAS to the air; 2) ensure drinking water treatment systems and remediation systems being designed to remove PFOA and PFOS are able to also consider employing treatment that can remove other PFAS compounds and associated degradates, some which could be precursors to the formation of PFOA and PFOS. Granular activated carbon is the standard treatment technology for PFOA and PFOS, but is not as effective in removing some of the shorter chain PFAS compounds or precursors to PFOS and PFOA. This information is critical for ensuring drinking water is appropriately treated and that remediation systems removing PFOA and PFOS do not unknowingly redistribute other PFAS contaminants; 3) differentiate sources of contamination when and where there is the potential for multiple sources of contamination by identifying a signature of distribution of compounds for different sources of PFAS; 4) assess if conditions warrant the installation of treatment systems for air emissions to proactively prevent the contamination of the environment and drinking water with the newer alternative chemicals or precursor compounds; 5) prioritize what contaminant(s) need a risk assessment based on what is actually being measured in the environment, including drinking water.
We greatly appreciate your assistance on this matter. We look forward to our continued partnership in successfully addressing these emerging drinking water contaminants. Please do not hesitate to contact me ([email protected], (603)271-8806) or Brandon Kernen ([email protected], (603)271-0660) should you have any questions.
cc: Meghan Cassidy, USEPA Region 1 Andy Lindstrom, USEPA ORD Michael Wimsatt, NHDES Eugene Forbes, NHDES Brandon Kernen, NHDES
eise Assistant Commissioner
Appendix A-2
Work Plan #1- Southern New Hampshire Sample Collection Plan for Non-Targeted Per- and Poly-fluorinated Compounds Analyses
August 30, 2017
Southern New Hampshire Sample Collection Plan for Non-Targeted Poly- and Perfluoroalkyl Substances (PFAS) Analyses
August 30, 2017
1.0 Objective
The objective of this sampling program is to identify the occurrence of the full spectrum of poly- and perfluoroalkyl substances (PFAS) in process feedstocks, product residuals, air emissions, surface water, groundwater and soil near two textile manufacturing facilities in southern New Hampshire. The identification of PFAS compounds will be completed by using a high resolution mass spectrometer at the United States Environmental Protection Agency's Office of Research and Development's lab at Research Triangle Park in Durham, NC. The information is needed to identify the specific PFAS compounds and their byproducts associated with air emissions that are being detected in the environment. NH DES will
use this information to identify other target PFAS compounds in an effort to expand commercial labs analyte lists.
2.0 Approach to Work
The approach to completing the work is described in Tasks 1-8, below. The sampling locations associated with each task are shown in figure attached as a file named "Figure."
Task 1 - Sample PFAS-Based Dispersion Products at Textile Coating Facilities
Samples of raw dispersion products consisting of PFAS compounds will be collected at two textile coating facilities. Products will be sampled at the Saint-Gobain Performance Plastics (SGPPL) facility in Merrimack, NH and the Textile Coating International (TCI) facility in Manchester, NH . These thirteen
dispersions represent all the raw dispersions currently in use at the two facilities .
Task 2- Sample Char/Carbon Material Taken from Air Emission Towers at SGPPL
Three samples of solid materials that accumulate on the interior of the towers will be collected and are
summarized as follows:
• One sample from the MA Tower which has been in operation at SGPPL since 1994. The ductwork was replaced and the oven and ancillary process components were cleaned in 2016. Therefore,
the solid material that will be collected from this stack will most likely represent new dispersions
used since 2016.
• One sample from the MS Tower which has been in operation at SGPPL since 2002. The solid material that will be collected from this stack may potentially contain residue components from pre-2006 PFOA based dispersions AND new dispersions that have been used since 2006.
• One sample from the QX Tower which has been in operation at SGPPL since 1989. This tower has the highest PFOA partition factor based on previous stack test results and therefore potentially
Page 1 of 3
receives the highest load of emissions. The solid material that will be collected from this stack may potentially contain residue components from pre-2006 PFOA based dispersions AND new dispersions that have been used since 2006.
Summaries of analytical data associated with the dispersion materials and char material are included in the file named "Task 2 Attachments." 1
Task 3 - Sample Highly Contaminated Groundwater and Soil Immediately Downgradient of the SGPPL Facility
A water sample will be collected from a shallow groundwater monitoring well immediately adjacent to and downgradient of the SGPPL property. A soil boring will be advanced 6-8 feet deep and approximately four soil profile samples will be collected .
Summaries of analytical data associated with groundwater and soil sampling at the SGPPL facility are included in the file named "Task 3 Attachments."
Task 4 - Surface Water Sampling
One water sample will be collected from the stormwater outfall that discharges stormwater from the SGPPL facility to the Merrimack River. Two samples of surface water will be collected from the Merrimack River up gradient and downgradient of the facility. Two water samples will be collected from Dumpling Brook which flows into the Merrimack River near the SGPPL property.
A summary of analytical data associated with the storm water outfall associated with the SGPPL facility is included in the file named "Task 4 Attachments." Water quality data for the Merrimack River and Dumpling Brook have not been collected to date.
Task 5 - Groundwater Sampling- Wells with Groundwater Exceeding 200 Parts-Per-Trillion PFOA
Groundwater samples will be collected from four private wells near SGPPL that exceed 200 Parts-Per Trillion (ppt) for PFOA.
A summary of analytical data for all of the potential private wells that meet this criterion is included in the file named "Task 5 Attachments."
Task 6 - Groundwater Sampling - Wells with PFOA Concentrations between SO and 100 ppt PFOA
Groundwater samples will be collected from four private wells located within three miles of the SGPPL facility that exhibit PFOA concentrations between 50-100 ppt. A summary of analytical data for all of the potential private wells that meet this criterion is included in the file named "Task 6 Attachments ."
The sample numbering in the Task 2 Attachments do not necessarily correspond to the sample numbering used in this exercise.
Page 2 of 3
Task 7 - Groundwater Sampling - Wells With Elevated PFOA and PFOS Concentrations and Located
Near Additional Sources of PFAS Contamination
Groundwater samples will be collected from six private wells that exhibit a combined concentration of PFOA and PFOS above 70 ppt and are located in areas that are: 1) Likely impacted by PFAS releases to air associated with SGPPL; and 2) Alleged to be potentially impacted by additional potential sources of PFAS.
A summary of analytical data for all of the potential private wells that meet this criterion is included in the file named "Task 7 Attachments ."
Task 8 - Groundwater Sampling - Merrimack Village District Wells 4 and 5 A groundwater sample will be collected from both Merrimack Village District (MVD) Well 4 and MVD Wells.
A summary of analytical data for MVD 4 and MVD 5 is included in the file named "Task 8 Attachments."
The following types and quantities of samples will be collected for each project task.
Groundwater Surface
Soil Char Material from Raw Dispersions
Water Tower Stacks
Task 1 13
Task2 3
Task 3 1 4 Task4 5
Task 5 4 Task 6 4 Task 7 6
Task 8 2
Task 9
Total 17 5 4 3 13
Total Number of Samples»> 42
3.0 Sampling Procedures and Quality Assurance Project Plan
NH DES' Quality Assurance Project Plan (QAPP) is included as an attached file. The procedures for sampling for PFAS in the QAPP begin on document page 246. Additional information describing the soil sample collection methodology is included in an attached file.
4.0 Schedule
The sample collection for Tasks 1-8 described in this work plan shall be completed from August 28, 2017 - September 22, 2017. Sampling for tasks 1-8 will occur concurrently.
Page 3 of 3
Appendix A-3
NH DES Letter- New Hampshire Department of Environmental Services Request for Additional Assistance Assessing Poly- and Perfluoroalkyl
Substances October 27, 2017
October 27, 2017
Timothy H. Watkins
The State of New Hampshire
Department of Environmental Services
Clark B. Freise, Assistant Commissioner
Acting Director, National Exposure Research Laboratory USEPA Office of Research and Development 109 TW Alexander Dr MC 305-01 RTP, NC 27711
Subject: New Hampshire Department of Environmental Services Request for Additional Assistance Assessing Poly- and Perfluoroalkyl Substances
Dear Mr. Watkins:
The New Hampshire Department of Environmental Services (NHDES) is requesting additional assistance for completing analyses of long and short-chain poly and perfluoroalkyl substances {PFAS) in industrial coating formulations and air emissions taken directly from the stacks located at a site where processes are currently utilizing PFAS-containing raw materials. This site has historically released PFAS into the environment and has contaminated soil and water, including groundwater used as drinking water for tens of thousands of people in the state. NH DES is concerned that ongoing air emissions of certain PFAS may be occurring in the absence of air pollution controls.
NH DES is currently using commercial laboratories to complete analyses that report results of 14 to 23 traditional PFAS compounds. NHDES has attempted to coordinate with a laboratory to analyze for a shorter chain PFAS compound variant that was reported to have replaced PFOA at the above reference facility. Despite analyzing over 1,000 samples from private and public drinking water wells in an area where groundwater has been contaminated with PFOA, this replacement compound has yet to be detected in water near this site. However, the replacement compound was detected in previous stack samples at the site and has been detected associated with other sites elsewhere in the country.
Assistance from the United States Environmental Protection Agency {USEPA) is needed to test for environmental contaminants that are potentially being released to the air and impacting the environment. USEPA's assistance is needed to overcome technical barriers for completing this work to date including: 1) commercial laboratory analytical limitations for handling more complex sample matrices; 2) unknown nature of the compounds because they are proprietary, manufacturing byproducts or degradation compounds contained in raw materials; and 3) lack of expertise and experience associated with advanced fluorochemistry and its fate and transport properties. USEPA could assist by analyzing samples using high resolution mass spectrometry with a comprehensive assessment of the spectral data using library searches.
www.des.nh.gov 29 Hazen Drive• PO Box 95 • Concord, NH 03302-0095
(603) 271-3503 • Fax: 271-2867 • TDD Access: Relay NH 1-800-735-2964
Timothy H. Watkins USEPA Office of Research and Development October 27, 2017 Page 2 of 2
NH DES will utilize this information to: (1) Understand the current emissions of fluorinated compounds generated when utilizing current
chemical formulations; (2) Assess if conditions warrant the installation of treatment systems for air emissions to
proactively prevent the contamination of the environment and drinking water with the newer alternative chemicals or precursor compounds;
(3) Ensure any potential air pollution control equipment systems that may be required to be installed are designed to remove not only PFOA aryd PFOS compounds but also any other PFAS compounds and associated degradates, some which could be precursors to the formation of PFOA and PFOS. This information is critical for ensuring any air pollution control equipment is properly designed for potential PFAS emissions and that remediation systems removing PFOA and PFOS do not unknowingly redistribute other PFAS contaminants;
(4) Differentiate sources of contamination when and where there is the potential for multiple sources of contamination by identifying a signature of distribution of compounds for different sources of PFAS; and
(5) Prioritize what contaminant(s) need a risk assessment based on what is actually being measured in the environment via the air emission pathway.
We greatly appreciate your assistance on this matter. We look forward to our continued partnership in successfully addressing these emerging drinking water contaminants. Please do not hesitate to contact me ([email protected], (603)271-8806) or Catherine Beahm ([email protected], (603) 271-2822) should you have any questions.
cc: Meghan Cassidy, USEPA Region 1 Andy Lindstrom, USEPA ORD Michael Wimsatt, NHDES Lea Anne Atwell, NHDES Eugene Forbes, NHDES Brandon Kernen, NHDES Michael Fitzgerald, NHDES Cathy Beahm, NHDES
Assistant Commissioner
Appendix A-4
Work Plan #2 - Saint-Gobain Performance Plastics Air Sample Collection Plan for Non-Targeted Per- and Polyfluoroalkyl Substances Analysis
April 18, 2018
Saint-Gobain Performance Plastics Air Sample Collection Plan for Non-Targeted Perand Polyfluoroalkyl Substances Analyses
April 18, 2018
1.0 Objective
The objectives of this sampling program are to identify the full spectrum of per- and polyfluoroalkyl
substances (PFAS) in air emissions, process feedstocks, and process residuals from Saint-Gobain
Performance Plastics (SGPPL) in Merrimack, New Hampshire and to assess the performance of a
candidate pilot-scale air pollution control system. The identification and possible quantification of PFAS
compounds will be conducted using multiple GC/LC/mass spectrometric techniques (e .g. low and high
resolution time of flight preceded by gas chromatography separation and tandem mass spec preceded
by liquid chromatography separation). These analyses will be conducted at the United States
Environmental Protection Agency's Office of Research and Development (ORD) laboratories located at
Research Triangle Park, North Carolina and Athens, Georgia .
The results of the program will be used to identify the specific PFAS compounds and related byproducts
associated with air emissions and compounds that are being detected in the environment. NHDES will
utilize this information to:
(1) Document emissions of fluorinated compounds utilizing current chemical formulations;
(2) Determine whether conditions warrant the installation of air pollution controls to prevent the
environmental impact with the next generation of raw materials;
{3) Ensure that a pilot scale air pollution control system is designed to effectively control PFAS and
associated analogues, some of which are known precursors to the formation of PFOA and PFOS.
(4) Develop "source type signatures" to differentiate multiple sources of contamination; and
(5) Develop risk based prioritization procedures for evaluating air emissions (both deposition and
inhalation pathways) for contaminant(s) measured in the environment.
2.0 Approach to Work
The approach to completing the work is described in Tasks 1-4, below. The sampling locations
associated with each task are shown in the Figures 3 - 5 of the attached SGPPL Stack Test Plan dated
April 11, 2018.
Page 1 of 5
Task 1 - Air Emission Samples
SGPPL has contracted with Barr Engineering to conduct the stack testing that will collect the air emission
samples. Barr Engineering will be using SGS Laboratories to prepare field reagents and perform
analytical work for SGPPL. NH DES staff will be on site during the stack testing to observe the entire test
program and SGPPL has agreed to collect additional samples1 for submittal to ORD for non-routine
analyses.
The combined program will involve the testing of one cast film and two fabric coating towers as listed
below:
• MA Tower - Emission samples from this fabric coating tower will be collected at the uncontrolled
exhaust prior to the dilution fan/exhaust stack.
• MS Tower - Emission samples from this fabric coating tower will be collected at the uncontrolled
exhaust prior to the dilution fan/exhaust stack.
• QX Tower - Emission samples from this cast film tower will be equipped with a pilot-scale wet
cyclone/fiberbed mist collection system (APCE). Emission samples will be collected
simultaneously at the inlet and outlet locations of the APCE.
A modified method 5 (MMS) train will be used to collect PFAS compounds with nominal boiling points
greater than l00°C. For the purpose of collecting samples for ORD, three 2-hour test runs2 will be
conducted for each tower location for a total of 12 sample sets. In addition, reagent blanks will be
collected for each MMS fraction and a field biased blank sampling train will be set up and recovered to
assess any field contamination issues.
Each MMS sample train consists of a nozzle, heated probe, heated glass fiber filter, XAD-2/Condenser
Module, three Greenberg-Smith impingers [one containing 100 ml DI water, one containing 100 ml
0.lN sodium hydroxide (NaOH), and one containing 0.0lN sodium borate], a second unheated filter
followed by an indicating silica gel impinger for water vapor removal. Since each train has 6 fractions
plus a methanol (MeOH) rinse fraction, there will be a total of 7 fractions per sampling train for a total of
98 samples to be analyzed separately.
Summa Canisters will be used to collect volatile compounds with boiling points less than 100°C. Canister
samples will be collected during each of the 2-hour test runs summarized above . Sampling will be
conducted in accordance with the methodology specified in EPA's Compendium of Methods for the
Determination of Toxic Organic Compound - T014A and T015. Canister orifices will be adjusted to
Since the tower ductwork is anticipated to be less than 24 inches in diameter, concurrent sampling following standard EPA methodology is prohibitive. Therefore, a total of 6 test runs will be conducted for each tower sample location with every other test run sent to ORD and the remaining sent to the commercial lab (SGS Laboratory) . Test runs will be two hours in duration unless labs state that longer timeframes are required for lower detection limits.
Page 2 of 5
collect integrated samples during the specified 2-hour test period. NH DES will conduct the sampling
according to EPA's Miscellaneous Operating Procedure (MOP) that will be provided as part of the
Summa Canister shipment. A total of 12 samples, 1 field blank and 3 ambient locations (TBD) will be
collected .
The industry standard when conducting stack testing using sampling trains involving resins is for the test
company to send the glass resin traps and glass fiber filters to the lab conducting the sample analyses.
The lab cleans the glass traps according to their QC protocol, prepares and QCs the resin batch (in this
case XAD-2), packs the resin traps, spikes the traps with surrogates to assess recovery and ships the
sampling media to the field for the sampling team to use. Similarly, the laboratory may QC the filter
media/reagents and/or pre-clean the filters and provide these reagents to the sampling team. This is
important because the sampling company must choose glass traps that are compatible with their
sampling equipment. Also, on past tests for PFAS, the lab provided the other reagents that were QC'd as
is the case with the XAD. This included the DI water, 0.lN NaOH, MeOH, 0.0lN sodium borate, pre
cleaned glass fiber filters and sample recovery bottles.
In this case, there are two labs conducting the post-testing analyses: ORD and SGS Laboratories.
Therefore, it is imperative that coordination of the pre-test preparation work be facilitated in a way that
all parties are aware of the details and schedule. Barr Engineering will provide XAD glassware to SGS
Laboratories for cleaning, packing resin, and spiking and SGS will provide the reagents for samples that
are QC'd. The field team will collect reagent blanks in the field and assemble and recover a field-biased
blank train to account for any handling bias during one of the test runs.
ORD will provide a surrogate mixture to SGS and SGS will add this surrogate mixture as a field spike to
the resin traps designated for the ORD sample sets. These traps will be spiked with the labeled
compounds listed below:
Compound
Perfluoro-n-[3,4,5-13C3]pentanoic acid
Perfluoro-n-[l,2-13C2]decanoic acid
Perfluoro-n-[1,2,3,4-13C4]octanoic acid
Sodium perfluoro-1-[1,2,3,4-13C4 ]octanesulfonate
2-Perfluorohexyl-[l,2-13C2]-ethanol (6:2)
2,3 ,3 ,3-Tetrafluoro-2-( 1, 1,2,2,3 ,3 ,3-heptafl uoropropoxy)-13C3-
propanoic acid
Page 3 of 5
Abbreviation
M3PFPeA
MPFDA
MPFOA
MPFOS
M2FHET
M3HFPO-DA
Task 2 - Sample PFAS-Based Raw Materials
Samples of raw materials thought to contain PFAS compounds were collected at this facility as part of
the initial ORD sampling project in the fall of 2017. Based on process information submitted by SGPPL
to NH DES, the raw materials that are planned to be used at the time of the stack testing are the same as
those already sent to ORD. The actual coating formulations used at the time of the stack test will be
collected from each dip pan(s) on each tower during each test run and sent to ORD for analysis. At a
minimum, 1 sample from the dip pan from the MA and MS Towers for each of the stack test runs will be
collected, for a total of 6 samples from these two towers. At a minimum, 1 sample from each dip pan
from the QX Tower for each of the stack test runs will be collected. Since the QX Tower will be operated
using four passes, there will be 4 samples for each stack test of the QX Tower for a total of 12 samples .
In total, ORD will receive 18 dip pan samples.
Task 3 - Sample Char/Carbon Material Taken from Air Emission Towers
Three samples of solid materials that accumulate on the interior of the towers were collected as part of
the initial ORD sampling project in the fall of 2017 . Three additional samples of this material will be
collected during the stack testing program and are summarized as follows :
• One sample from the MA Tower which has been in operation at SGPPL since 1994. The ductwork
was replaced and the oven and ancillary process components were cleaned in 2016. Therefore,
the solid material that will be collected from this stack will most likely represent new dispersions
used since 2016.
• One sample from the MS Tower which has been in operation at SGPPL since 2002. The solid
material that will be collected from this stack may potentially contain residue components from
pre-2006 PFOA based dispersions AND new dispersions that have been used since 2006.
• One sample from the QX Tower which has been in operation at SGPPL since 1989. This tower has
the highest PFOA partition factor based on previous stack test results and therefore receives the
highest load of emissions. The solid material coating the interior of the tower would likely be
associated with emissions that occurred while PFOA-based dispersions were in use and emissions
that occurred after the use of PFOA had been phased out.
Task 4 - Sampling of the Pilot-Scale Air Pollution Control Equipment (APCE)
SGPPL is planning on conducting a pilot-scale evaluation of a candidate air pollution control technology
on the QX Tower in addition to collecting samples for ORD. Inlet and outlet samples will be collected as
described under Task 1 above.
Page4of5
The candidate APCE is a wet cyclone/fiberbed mist collection system. Gas enters the unit and passes
through a wet cyclone where larger particles are removed. The material that is removed falls into the
cyclone sump and the water in the sump is recirculated through the cyclone. In a full scale system, the
sump has a makeup water feed and a slow solids removal cycle for higher solids applications. In the case
of water soluble PFAS, the situation exists where the PFAS concentrations in the water could exceed the
solubility of the sump liquid if the makeup water input is not sufficient.
The filter system is a spun fiber type (depth filter type) and would not normally have a pulse system to
clean the surface of collected particulate . Any particulate that is not embedded in the filter structure
drops to the hopper and the fine particles enter the depths of the filter. At some point, the filter plugs
and must be changed.
In conjunction with the APCE evaluation and in addition to the air samples, NHDES will collect samples of
the make-up water (from plant water source - 1 sample), sump water (for each of the three APCE test
runs on QX Tower - 3 samples) and any solid matter that can be removed from the internals of the unit
after the test is done and the unit is taken offline (e.g. sump solids, particulate filter material - 2
samples).
The following types and quantities of samples will be collected for each project task:
Air Emission Summa Canister Dip Tank Char Material Process Water
from Tower and Solids from Samples Samples Coatings
Stacks APCE
Task 1 98 16
Task 2 18
Task 3 3
Task4 6
Total 98 16 18 3 6
Total Number of Analytical Fractions 141
3.0 Sampling Procedures and Quality Assurance Project Plan
NHDES' Quality Assurance Project Plan (QAPP) was included in the initial ORD request package. The
procedures for sampling for PFAS in the QAPP begin on document page 246.
4.0 Schedule
The sample collection described in this work plan shall be conducted late April and early May, 2018.
Sampling for Tasks 1-4 will occur concurrently .
Page 5 of 5
Appendix A-5
Stack Test Plan Saint Gobain Performance Plastics Corporation Merrimack, New Hampshire
April 11, 2018
STACK TEST PLAN
SAINT GOBAIN PERFORMANCE PLASTICS CORPORATION MERRIMACK, NEW HAMPSHIRE
Date test plan created/revised/finalized:
March I, 2018 / April 2,2018 / April 11, 2018
April 26-27 and April 30-May 2, 20 I 8 Scheduled test date(s):
PART I. GENERAL INFORMATION
Name and address of emission facility:
Air Emission Facility ID Number:
Facility Contact:
Reason for the test:
Saint Gobain Performance Plastics Corporation 701 Daniel Webster Highway Merrimack, NH 03054
3301100165
Ed Canning (518) 345-2122 Director, Health, Safety & Environment
There are several objectives being undertaken in this stack test mobilization:
The first objectives are in response to the State of New Hampshire Department of Environmental Services (NHDES) request in a letter dated October 27, 2017 and subsequent meetings and conversations held since that time
I . Conduct Modified EPA Method 5 (MM5) stack emission testing on the MA and MS Coating Towers and the QX Cast Fi lm exhausts.
2. Dip pan samples of formulated dispersions will be taken during each stack test run.
3. Determine UCMR 3 List 1 PFAS compounds and GenX stack emissions from the MA and MS Coating Towers and the QX Cast Film exhaust and dispersion samples with analytical services provided by SGS Accutest.
4. Measure NHDES regulated toxic air pollutants (RT APs) ammonia and total fluorides as fluorine stack emissions from the MA Coating Tower exhaust. Samples to be submitted to Element One, Inc.
Additional objectives are included under the direction of Saint Gobain Performance Plastics
5. Conduct additional MM5 sample collection at the outlet of a coalescing fiberbed filtration control device to be installed on the QX Cast Film on a pilot basis for this test mobilization. This objective will be performed in
Testing Company and Contact:
concert with objective 1 above, in that the inlet and outlet of the control device will be tested simultaneously and the inlet measurement will represent uncontrolled emissions.
6. A sample of the incoming water supply to the control device will be taken at the beginning of the test. Control device water sump samples will be taken during each stack test run . These samples will be submitted to SGS Accutest.
7. Determine UCMR 3 List 1 PFAS compounds and GenX stack emissions from the MA and MS Coating Towers and the QX Cast Film exhaust samples with analytical services provided by SGS Accutest.
All tests will be conducted under representative operating conditions with product and product coatings to be determined prior to the test mobilization. The selected products and coatings will be submitted to NHDES under separate, confidential cover as Confidential Business Information (CBI).
The MA and MS tower processes are fabric coating applications involving a preparation of aqueous fluoropolymer dispersion coating, coating application to a glass cloth web in a dip pan, and finally heat treating in three stages-dry zone, bake zone and fuse zone. The products being manufactured require multiple coating and heat treating applications. The tests are usually conducted during the first coating pass, as the first pass is the heaviest application of coating. The formulated coating, consisting of aqueous fluoropolymer dispersion surfactants and other processing aids, is sampled at the drip pan during the tests. Hot gases captured from the three stages of heating are exhausted through the tower stack.
QX cast film production involves a multi-coat process where formulated dispersion is coated in a dip pan on a web at room temperature, and then passed through a vertical oven or tower, similar to the glass cloth coating process, where the water and is removed. The web path through the tower is typically vertical. Multiple dipping and drying/baking steps may be used to produce a multi- layer film that is peeled from the web, resulting in the final product. The film is sintered like other fluoropolymer products to achieve final characteristics. Once the final film layer is applied, the film is wound onto a roller.
Diagrams of the glass cloth coating and the cast film processes are provided in Figures 1 and 2, respectively. Stack test sample port locations are provided in Figures 3-5 .
Barr Engineering Co. (952) 832-2630 Tim Russell (612) 741-6889 mobile Vice President, Chemical Engineer [email protected] 4300 MarketPointe Drive, Suite 200 Minneapolis, MN 55435
2
Private Analytical Laboratories and Contacts:
PF AS and GenX analysis SGS Accutest (407) 425-6700 ext 2602 Norm Farmer (407) 595-9987 mobile Corporate Technical Director N [email protected] 4405 Vineland Rd Suite C-15 Orlando, FL 328 11
Ammonia and Total Fluorides analysis Element One Inc. Paula Smith 6319-D Carolina Beach Road Wilmington, NC 284 12
PART II. TESTING REQUIREMENTS
The tab le below provides a summary of the pollutants to be tested and test methods.
Source Limitation Pollutant Tested and Specific Methods Citation Description Basis of Applicable Emission
Pollutant Limit Tested
MA None Determine UCMR 3 EPA Methods 1-4
Coating List 1 PFAS
Modified EPA Method 5 (Three 2-hour test runs) Tower
compounds and
Exhaust GenX. See compound list below.
Total Fluorides EPA Method 13B (Three I-hr test runs) Ammonia EPA CTM 027 (Three I -hr test runs)
MS None Determine UCMR 3 EPA Methods 1-4
Coating List 1 PFAS
Modified EPA Method 5 (Three 2-hour test runs) Tower
compounds and
Exhaust GenX. See compound list below.
QX Cast None Determine UCMR 3 EPA Methods 1-4 Film Line List I PFAS
Modified EPA Method 5 (Three 2-hour test runs) (pilot compounds and control GenX. See compound EPA Method 2 airflow rates will be measured on device inlet li st below. the main stack once during each test run to and outlet) determine total airflow volume from the line.
Moisture content, gas composition and pollutant concentration wi ll be assumed equal to measurements made at the pi lot scale test inlet location. The sum of airflow measurements made
3
at the pilot scale test inlet and main stack will be used to calculate uncontrolled mass emissions from the line.
Fluorinated compound analyte list for SGS Accutest submitted samples:
Perfluorooctane Sulfonic Acid (PFOS)
Perfluorooctanoic Acid (PFOA)
Perfluorononanoic Acid (PFNA)
Perfluorohexane Sulfonic Acid (PFHxS)
Perfluoroheptanoic Acid (PFHpA)
Perfluorobutane Sulfonic Acid (PFBS)
2,3,3,3-Tetrafluoro-2-(heptafluoropropoxy)propanoic acid (GenX)
PF AS Detection Limits
SGS Accutest provided information regarding current detection limits for the compounds targeted in this
project. For most compounds, method detection limits (MDLs) are 0.0025 µg/1 and reporting limits (RLs)
are 0.0 JO µg/1. With that, a simple case of a I 00 ml liquid sample fraction from an impinger sample with
a typical air sample volume of 60 ft 3 in a two hour test run would have a detection limit of 0.59 ng/m3 at
the RL. Of course, the answer to the detection limit question becomes more complicated under the
chosen sampling and analytical methodology. Each test run will generate seven sample fractions that are
analyzed separately. For each test run, the reported total mass of a compound and resulting calculated air
concentration and mass emission rate for that compound is the sum of the values determined for each
sample fraction. The commonly accepted reporting convention is to add the values of all sample fractions
with a detectable quantity of the compound plus the value at the detection limit for fractions that are
non-detect and to quali fy the calculated sum with a"<" designation.
4
PART III. OPERATING CONDITIONS AND PROCESS SAMPLES
The table and paragraph below identifies the process equipment to be tested, the operating parameters to
be monitored and reported, and the rationale for testing.
Process Equipment Description for MA and MS Coating Towers Units to be Tested
Process Equipment Parameter Dispersion identification, di spersion application rate, web Monitoring During Performance Test width, line speed, coating pass number and oven zone
temperature information will be recorded during the test
Process Monitoring Frequency Continuously or at least every 15 minutes during test run
Personal Assigned to Record data Saint Gobain staff
Control Equipment Description These sources are uncontrol led
Control Equipment Operating Not applicable Parametei: During Performance Test
Process Samples Dispersion sample taken from dip pan
Sampling Frequency I sample per test run
Personnel Assigned to Collect Barr staff Samples
5
Process Equipment Description for QX Cast Fi lm Line Units to be Tested
Process Equipment Parameter Dispersion identification, dispersion application rate, web Monitoring During Performance Test width, line speed and oven temperature information will
be recorded during the test
Process Monitoring Frequency Continuously or at least every 15 minutes during test run
Personal Assigned to Record data Saint Gobain staff
Control Equipment Description Pilot scale coalescing fiberbed filter
Control Equipment Operating Quench water rate and pressure drop across pre-filter (if Parameter During Performance Test applicable) and fiberbed filter. Details to be adjusted
based upon pilot unit specifics and instrumentation package
Monitoring Frequency Start and every 15 minutes during test run
Personnel Assigned to Record data Saint Gobain or Barr staff
Process Samples Di spersion - QX process line utilizes multiple "dip pans". Each dip pan will be sampled individually during each test run. These samples will be collected and analyzed independently
Supply water
Scrubber Sump water
Sampling Frequency I sample per test run
Personnel Assigned to Collect Saint Gobain or Barr staff Samples
PART IV. TEST AND ANALYTICAL METHODS
The following is a description of the test methods, number of test runs, length of test runs, and sampling
rate for each analyte.
A. EPA Method I for the location of sampling ports and points. One determination per test location .
B. EPA Method 2 for stack gas velocity and volumetric flow rate. One determination per Modified
EPA Method 5 test run.
C. Modified EPA Method 3/3A to determine stack gas molecular weight. One determination per
Modified EPA Method 5 test run . Integrated gas samples of approximately 120 minutes will be
collected in Tedlar Bags during each test run from the exhaust of the dry gas meter. The dry stack
gas will be analyzed with a Servomex 1440 oxygen and carbon dioxide analyzer calibrated to
6
EPA Method 3N7E specifications. Ambient air or EPA protocol gas will be used for the oxygen
span gas upper value. CEMS grade nitrogen will be used to zero instrumentation. A)] other
calibration gases used will be EPA Protocol certified gases. An example calibration gas
certification is provided in the attachments.
D. EPA Method 4 for determination of moisture content in stack gas. One determination per
Modified EPA Method 5 test run .
E. EPA Method 5 Modified to collect perfluorinated compounds. The sample train will consist of a
sample nozzle and heated sample probe and three impingers in series followed by an unheated
glass fiber filter. The three impingers will be charged in order with 100 ml each of de-ionized
water, 0.1 N sodium hydroxide, and 0.01 N sodium borate buffer. Each of the five resulting sample
fraction s will be recovered and analyzed separately for the determination of total target analyte
mass. The filter will be collected separately from a methanol rinse of a)] components of the
sample train. The modification of Method 5 fol lows test protocols previously accepted by the
USEPA. A copy of the method, as published in the February 2005 QAPP for the Dispersion
Processor Mass Balance Study Project is attached. The modified method was written specifically
for the collection of APFO, but has since been utilized for sampling the class of compounds
included in this test. Sampling times will be three run s of 120 minute duration for each test.
Additional modifications are being made to this method for this test and are described below in
item F.
F. Additional modifications are being made to Method 5 sample train for this test in order to capture
semi-volatile PFAS compounds. A heated glass fiber filter will be added to the oven section of
the sample train followed by a water chilled coiled condenser, water chilled XAD2 resin trap and
a knockout impinger prior to the impinger array and fina l filter described above. The trap will be
spiked by SGS Acutest at 100 ng for M3PFPeA, M2PFDA, M2PFOA and M4PFOS. The heated
filter and resin trap will be collected and submitted for analysis as two additional sample fractions
for a total of 7 samples for submittal (front filter, XAD2 trap, DI impinger, sodium hydroxide
impinger, sodium borate impinger, back filter and all components of train methanol rinse). Water
collected in the knockout impinger will be combined with the DI impinger sample. A)]
components of the sample train will be rinsed with methanol. The silica gel impinger will be
weighed pre and post test runs and will not be stored in a container. Reagent blanks will be
collected multiple times during the sampling campaign. Train blanks will be collected for each
test location and will consist of setting up and recovery of complete sample train . Moisture
determinations from the sample trains wil l be determined gravimetrically. The following train
components will be weighed pre and post test run: XAD2 trap, knockout impinger, DI impinger,
7
0.1 sodium hydroxide impinger, 0.0 I sodium borate impinger, final filter assembly and the dry
column. All samples , with exception of dispersion samples, will be stored in cooled condition .
G. SGS Accutest of Orlando, FL will perform the laboratory analysis of the air impinger, dispersion
coating and control device water samples using high pressure liquid chromatography and tandem
mass spectrometry (LC/MS/MS) in accordance with EPA Method 537 modified to accommodate
the air emission testing procedures and to enhance method performance as per SGS SOPS .
H. EPA Method 13B Determination of total fluoride emissions. Gas stream will be sampled
isokinetically to account for possible water droplets or mist. Sampling times will be three runs of
60 minute duration for each test. The sampling train will be arranged and operated as described in
the method with filtration taking place after the third impinger. The reagent and recovery solvent
will be environmental grade water. The filter media will be Whatman # I as listed in the method
(See Method 13A 7.1.1 .1 ). Sample will be recovered into HDPE sample storage bottles. Reagent
blanks will be collected and analyzed. Temperature control of samples is not required for this
method. Description of the sample train, setup, operation, recovery and analysis are located in
EPA Method 13B. A copy of the method is not provided with this test plan submittal.
I. EPA Conditional Test Method (CTM) 027 Determination of ammonia emissions Modified. Gas
stream will be sampled isokinetically to account for possible water droplets or mist. Sampling
times will be three runs of 60-minute duration for the test. The sample train will be as operated
and arranged as described in the method, except that filtration will take place in oven. Filtration in
the oven was chosen as opposed to the in-stack approach in the described in the method due to
concerns of potential area blockage in small diameter stack. The probe and filter temperatures
will be operated at temperatures consistent with EPA Method 5. Thi s is expected to have no
impact on results since filterable portion is not analyzed. The sample train will consist of three
impingers as described in the method. Impingers one, two and three will be loaded with I 00 mis
O. lN sulfuric acid. The third impinger will be analyzed separately for determination of
breakthrough. Reagent blanks will be collected and analyzed. Temperature control of samples is
required for this method. The above exceptions, notwithstanding, the test description of the
sample train, setup, operation, recovery and analysis are located in CTM Method 027. A copy of
the method is not provided with this test plan submittal.
PART V. CALIBRATION METHODS AND PRETEST PREPARATIONS
A. The EPA Method 5 Equipment will be calibrated prior to the test in accordance with the
requirements in 40 CFR Part 60, Appendix A, EPA Quality Assurance Handbook for Air
8
Pollutant Measurement Systems: Volume III Stationary Sources Specific Methods and Barr
Standard Operating Procedures.
B. Pretest preparations for Modified Method 5 for PFAS compounds inc ludes cleaning and methanol
rinse of all sample train glassware components and the preparation of samp ling reagents. Special
care is made to eliminate all components of the sample train that may contain fluoropolymer
constituents in order to avoid trace contamination of the samples from those components.
Examples include avoiding the use of TeflonTM compression fittings or ferrules, sealing tape or
sample jar liners, and fluoropolymer encapsulated O-ring seals.
PART VI. QUALITY ASSURANCE AND LABORATORY STANDARD OPERATING PROCEDURES
A. SGS Accutest Orlando facility has developed standard operating procedures for use of EPA
Method 537 for the purposes of this project. The SOPs are considered to be proprietary business
information by SGS and can be shared upon execution of a confidentiality agreement.
B. A complete review of the analytical laboratory recoveries , duplicates, and raw data by a member
of Barr's Data Quality Assurance staff will be performed and presented in the test report.
PART VII. SAFETY
Emergency procedures are outl ined in Saint Gobain 's "Contractor Control Program" which can be
reviewed upon arrival at the facility. In the event of a medical, fire or other emergency response, dial 9 11
and then the company contact.
PART VIII. TEST SCHEDULE
Day I Day 2 Day 3 Day4 Day 5 Day 6
Monday T uesday Wednesday Thursday Friday Saturday
4/23 4/24 4/25 4/26 4/27 4/28
Travel Travel Faci lity Safety Test Towers Test Towers Move gear Meeting MA and MS
MA and MS from
Pretest MAIMS
Coordination Three test runs
toQX
Equipment Setup on each tower Three test runs inlet/outlet on each tower
9
Day7 Day 8 Day 9 Day 10
Sunday Mon Tuesday Wednesday
4/29 4/30 5/1 5/2
Day Test QX Cast Test QX Cast Test Tower MA Off Film inlet/outlet Film inlet/outlet Fluorides and
ammoni a RT AP
Three test runs Three test runs simultaneous at simultaneous at Three I -hr test
each test location each test runs per test (six location runs total)
Typical Daily Test Schedule:
0700
0800
0800-1 000
!000-11 00
1100-1300
1300-1400
1400-1600
Barr staff arrive and process is running at this time
Target test start time
Test Run 1
Sample recovery
Test Run 2
Sample recovery
Test Run 3
10
Day 11 Day 12
Thursday Friday
5/3 5/4
Travel Travel
PART IX. TEST REPORT
One complete test report will be submitted within 45 days of receipt of the full and final laboratory data
report.
Submjttal Address:
Attachments:
Mr. Ed Peduto
Sr. Compliance Assessment Engineer
Air Resources Division - Compliance Bureau
New Hampshire Department of Environmental Services
29 Hazen Drive
Concord, NH 03301
(603 ) 271-1987
Edward [email protected]
Standard Operating Procedure- Particulate and Condensable Matter Sampling for Ammonium
Pertluoro-octoanate in Stack Emissions
Figure I - Typical Glass Cloth Process Diagram
Figure 2 - Typical Cast Film Process Diagram
Figure 3 - Test port locations Tower MA exhaust
Figure 4 - Test port locations Tower MS exhaust
Figure 5 - Test port locations QX cast film pilot control device inlet/outlet
Example Calibration Gas Certification
11
STANDARD OPERATING PROCEDURE
Particulate and Condensable Matter Sampling for Ammonium Perfluoro-octoanate in Stack Emissions
1.0 Scope and Application
This Standard Operating Procedure (SOP) is applicable to gas streams flowing in ducts, stacks and flues
for the determination of average flow velocity, moisture content, gas molecular weight (carbon dioxide
(CO2), oxygen (02) content) and ammonium perfluoro-octoanate (APFO) content in particulate and
condensable matter in stationary sources.
This SOP is primarily based on USEPA Method 5, however it also incorporates procedures from USEPA
Methods 1, 2, 3, 3A, and 4. It is the responsibility of the team leader/project manager to read and
understand the EPA Methods referenced.
2.0 Summary of Method
A representative measurement site is selected and stack gas is withdrawn isokinetically from the source
and collected in a heated sample probe, a series of chilled glass impingers and on a glass fiber filter
maintained at ambient temperature. The APFO mass is determined analytically; which includes any
material that condenses at the operating temperatures of the sampling train , is scrubbed or fi ltered from
the sample, or combines chemically with the sample train absorbing solutions.
3.0 Equipment and Supplies
3.1 Airflow Velocity
Stainless steel standard and type S Pitot Tubes of various lengths
Calibrated Pyrometer
Water for Wet Bulb
Calibrated Thermocouples
Calibrated Barometer
Calibrated differential pressure measurement devices
Tape Measure
Duct tape
Sharpie Marking Pens
High temperature fiberglass tape
Wet Bulb Wicks
12
Spare batteries for pyrometer and electronic manometers
Protractor for Cyclonic Flow Determinations
3.2 APFO Sampling
Stainless Steel Probes/Pitot tube assemblies (various lengths that include the probe sheath, S-type pitot
tube, and stack temperature thermocouple)
Sample Modules (heated oven box and impinger ice bath) Umbilical (various lengths between 50 and 200
feet) Control Modules
Vacuum Pumps
Lab Box : Containing probe cleaning brush, field balance, sample recovery solvent wash bottles,
desiccant, sample nozzle set with calipers for field validation of nozzle opening diameter and supply of
compression fittings and ferrules for probe/nozzle union, 2- IO" crescent wrenches, 3- 250 ml
polyethylene graduated cylinders, supply of deionized water (for purposes of this SOP when deionized
water is referred to it means Type I water that has been treated with Hypercarb to remove traces of
APFO), supply of acetone (for purposes of this SOP when acetone is referred to it means Optima Grade
Acetone or equivalent), sample bottle label s, supply of pump and manometer oils, size O and 00 rubber
stoppers, field portable pH meter and pH paper, duct tape, high temperature fiberglass tape, stopcock
grease (acetone-insoluble, heat-stable silicone grease) , neoprene gloves, leather and cloth work cloves,
Kim wipes, spare fuse supply for control module, tape measure, ¼" I.D latex tubing, spare silicone O
rings for ground glass ball fittings on glassware.
Glassware Box: containing glass filter holder assemblies, glass filter frits with silicone gaskets, filter
cyclones and Erlenmeyer flasks, filter and cyclone bypass glassware, a supply of clean glass fiber filters
in styrene Petri dishes, filter forceps , nylon bristle brushes and rubber policeman for sample recovery, size
0 and 00 rubber stoppers to seal glassware openings, Kim wipes.
Impinger sets (ball and socket type with silicone O-ring seals) with connecting u-tube glassware and
glassware clamps.
Monorails and port clamps
Polyethylene
Sample containers
13
Tap Water
Toweling (cloth and fiberglass cloth) to seal sample ports during sample runs .
Probe Liners. Borosi licate or quartz glass tubing with a heating system capable of maintaining a probe gas
temperature of (248 ± 25°F) during sample performance.
Supply of 0.1 N NaOH, 0.0 IN Na2B4O7 buffer solution, and methanol sampling reagents . Both the
NaOH solution and the buffer solutions will be prepared in the laboratory using Type] Water that has
been treated with Hypercarb to remove traces of APFO. For purposes of this SOP, when methanol is
referred to it means Optima Grade Methanol or equivalent.
Crushed or cubed ice.
3.3 CO2, 02 Determination
Field portable oxygen meter to monitor oxygen content of the exhaust of the EPA Method 5 sample train
during sample collection .
Leak-free bags (5-40 liters in size, Tedlar or similar construction) for the collection of integrated stack gas
samples from the exhaust of the EPA Method 5 sample train during each sample run.
Orsat analyzer with reagent (oxygen absorbent and carbon dioxide absorbent) supply to support the
performance of EPA Method 3 or oxygen/carbon dioxide gas analyzer(s) for EPA Method 3A. The choice
of EPA Methods 3 or 3A is left to the discretion of the team leader.
Gas manifold for the introduction of calibration gas and the integrated gas sample for use with
oxygen/carbon dioxide gas analyzer(s) in accordance with EPA Method 3A.
EPA Protocol I calibration gas mixtures for use with oxygen/carbon dioxide gas analyzer(s) in
accordance with EPA Method 3A. Ambient air may be used as upper span gas for oxygen analyzer
calibration. CEMS grade nitrogen will be used for both oxygen and carbon dioxide instrument zero.
3.4 Moisture Determination
Same as APFO sampling equipment. The moisture determination is an intrinsic part of the APFO sample
collection method and will be performed during each sample run.
14
3.5 General Equipment
Extension cords (50 and I 00 foot lengths) Li ghts
Shelter (tent) fo r outdoor sampling locations
Heater for cold weather sampling locations
Folding table and chair fo r equipment setup
Ropes (50-150 feet in length as needed) to raise and lower equipment to sample platforms
Pl astic trash bags
Briefcase with copies of necessary fi eld data sheets, clipboard, calcul ator, pens.
Laptop computer for field data entry using spreadsheet fo r EPA Method 5 calculations
Duct Tape
Tools
T wo-way radios
Polyethylene Tubing ( 1/4" O.D.)
Supply of compression fittings
Sample Cooler Ice Cooler
3.6 Safety Equipment
Hot gloves
Cold weather gear as needed
Hard Hats (with visors for spl ash protection as needed)
Protective coverall s and gloves as dictated by conditions at each sample locati on
Ear Plugs
Safety Footwear
Respiratory protection
Portable Eyewash
First Aid Kit
Safety Glasses
Harness and lanyard(s) as required to work safely at each sampling location
4.0 Procedure
4.1 Selection of Measurement Site
4.1.1 Sampling and/or velocity measurements are performed at a site located at least eight stack or duct
diameters downstream and two diameters upstream from any flow disturbance such as a bend, expansion,
15
or contraction in the stack, or from a visible flame. If necessary, an alternative location may be selected,
at a pos ition at least two stack or duct diameters downstream and a half diameter upstream from any flow
disturbance. The procedure to select the measurement site is performed once for each sampling location.
4.1.2 Particulate Traverses
4.1.2.1 When the eight- and two-diameter criterion can be met , the minimum number of traverse
points shall be: (]) twelve , for circular or rectangular stacks with diameters (or equivalent diameters)
greater than 0.61 meter (24 in .); (2) eight, for circular stacks with diameters between 0.30 and 0.61 meter
( 12 and 24 in. ); and (3) nine, for rectangular stacks with equivalent diameters between 0.30 and 0.61
meter ( 12 and 24 in.).
4.1.2.2 When the eight- and two-diameter criterion cannot be met, the minimum number of
traverse points is determined from Figure 1-1 in EPA Method l ( 40 CFR Part 60 Appendix A). Before
referring to the figure, however, determi ne the distances from the measurement site to the nearest
upstream and downstream disturbances, and divide each di stance by the stack diameter or equivalent
diameter, to determine the distance in terms of the number of duct diameters. Then, determine from
Figure 1-1 the minimum number of traverse points that corresponds:(]) to the number of duct diameters
upstream; and (2) to the number of diameters downstream. Select the higher of the two minimum
numbers of traverse points, or a greater value, so that for circular stacks the number is a multiple of 4, and
for rectangular stacks, the number is one of those shown in Table 1-1 in EPA Method I ( 40 CFR Part 60
Appendix A).
4.1.3 Cross-Sectional Layout and Location of Traverse Points.
4.1.3.1 Circular Stacks.
4.1.3.1.1 Locate the traverse points on two perpendicular diameters according to Table 1-2
in EPA Method 1 (40 CFR Part 60 Appendix A).
4.1.3.1.2 For particulate traverses, one of the diameters must coincide with the plane
containing the greatest expected concentration variation (e.g., after bends) ; one diameter shall be
congruent to the direction of the bend.
4.1.3.1.3 In addition, for elliptical stacks having unequal perpendicular diameters, separate
traverse points shall be calculated and located along each diameter. To determine the cross
sectional area of the elliptical stack, use the following equation :
16
Square Area = Dl x D2 x 0.7854
Where:
DI = Stack diameter I
D2 = Stack diameter 2
4.1.3.1.4 In addition, for stacks having diameters greater than 0.6 I m (24 in. ), no traverse
points shall be within 2.5 centimeters (1.00 in.) of the stack walls; and for stack diameters equal to
or less than 0.61 m (24 in. ), no traverse points shall be located within 1.3 cm (0.50 in. ) of the stack
walls.
4.1.4 Stacks with Diameters Greater Than 0.61 m (24 in.).
4.1.4.1 When any of the traverse points as located in Section 11.3.1 fal l within 2.5 cm ( 1.0 in .) of
the stack walls, relocate them away from the stack walls to: (I ) a distance of 2.5 cm (1.0 in.); or (2) a
distance equal to the nozzle inside diameter, whichever is larger. These relocated traverse points (on each
end of a diameter) shall be the "adjusted" traverse points.
4.1.4.2 Whenever two successive traverse points are combined to form a single adjusted traverse
point, treat the adjusted point as two separate traverse points, both in the sampling and/or ve locity
measurement procedure, and in recording of the data.
4.1.5 Stacks With Diameters Equal To or Less Than 0.61 m (24 in.).
Follow the procedure in Section 4.1.3.1, noting on ly that any "adjusted" points should be relocated away
from the stack walls to: (1) a distance of 1.3 cm (0.50 in .); or (2) a distance equal to the nozzle inside
diameter, whichever is larger.
4.1.6 Rectangular Stacks.
4.1.6.1 Determine the number of traverse points as explained in Sections 4. 1.2. 1 and 4. L.2.2 of
this SOP. From Table 1- 1, determine the grid configuration. Divide the stack cross-section into as many
equal rectangular elemental areas as traverse points, and then locate a traverse point at the centroid of
each equal area accordi ng to the example in Figure 1-4 in EPA Method 1 (40 CFR Part 60 Appendix A).
4.1.7 Verification of Absence of Cyclonic Flow.
4.1.7.1 In most stationary sources, the direction of stack gas flow is essentially parallel to the
stack wall s. However, cyclonic flow may exist ( I) after such devices as cyclones and inertial demisters
17
following venturi scrubbers, or (2) in stacks having tangential inlets or other duct configurations which
tend to induce swirling; in these instances, the presence or absence of cyclonic flow at the sampling
location must be determined. The following techniques are acceptable for this determination.
4.1.7.2 Level and zero the manometer. Connect a Type S pitot tube to the manometer and leak-
check system. Position the Type S pitot tube at each traverse point, in succession, so that the planes of the
face openings of the pi tot tube are perpendicular to the stack cross- sectional plane; when the Type S pi tot
tube is in this position, it is at "0° reference." Note the differential pressure (dp) reading at each traverse
point. If a null (zero) pitot reading is obtained at 0° reference at a given traverse point, an acceptable flow
condition exists at that point. If the pitot reading is not zero at 0° reference, rotate the pi tot tube (up to
±90° yaw angle), until a null reading is obtained. Carefully determine and record the value of the rotation
angle to the nearest degree. After the null technique has been applied at each traverse point, calculate the
average of the absolute values of the rotation angle; assign values of 0° to those points for which no
rotation was required, and include these in the overall average. If the average value of is greater than 20°,
the overall flow condition in the stack is unacceptable, and alternative methodology, subject to the
approval of the Administrator, must be used to perform accurate sample and velocity traverses.
4.1.8 Data Analysis and Calculations.
Nomenclature.
L = length
W = width.
4.1.8.1 For a rectangular cross section, an equivalent diameter (De) shall be calculated using the
following equation, to determine the upstream and downstream distances:
De = 2 (L) (W)/(L + W)
4.2 Determination of Stack Gas Velocity and Volumetric Flow Rate (Type S Pitot Tube)
4.2.1 Set up the apparatus as shown in Figure 2-1 in EPA Method 2 ( 40 CFR Part 60 Appendix A).
Perform a leak-check be conducted as follows: ( 1) blow through the pi tot impact opening until at least 7.6
cm (3.0 in.) H20 velocity head registers on the manometer; then , close off the impact opening. The
pressure shall remain stable for at least 15 seconds; (2) do the same for the static pressure side, except
using suction to obtain the minimum of7.6 cm (3.0 in.) H20.
18
4.2.2 Level and zero the manometer. Check level at least once per hour. Record all necessary data on
data sheet.
4.2.3 Measure the velocity head and temperature at the traverse points. Ensure that the proper
differential pressure gauge is being used for the range of dp values encountered. Conduct a post-sample
leak-check as described in Section 4.2.1 above, to validate the traverse run. An initial velocity traverse
will be conducted at each sampling location to support the selection of the appropriate sample nozzle for
the modified Method 5 APFO isokinetic sampling method. Each of three APFO sample runs conducted at
each location will include the determination of stack gas velocity and volumetric flow rate.
4.2.4 Measure the static pressure in the stack. One reading is usually adequate per location.
4.2.5 Determine the atmospheric pressure at the meter console location.
4.2.6 Determine the stack gas dry molecular weight using the procedures described in Section 4.3. The
team leader can assume a gas composition of 20.9% oxygen, 0.0% carbon dioxide and the balance
nitrogen for non-combustion sources that utilize ambient air in the industrial process. The team leader can
also assume a gas composition consistent with past experience on similar sources as an initialization
parameter for the modified Method 5 APFO sampling method.
4.2. 7 Obtain the moisture content from using procedures described in Section 4.4. The team leader can
use the alternative determination of moisture content using wet-bulb/dry-bulb temperature measurements
as an initialization parameter for the modified Method 5 APFO sampling method.
4.2.8 Determine the cross-sectional area of the stack or duct at the sampling location. Measure each
diameter distance to verify its dimensions.
4.3 Gas Analysis for the Determination of Dry Molecular Weight
4.3.1 Perform the following procedures before measurement of emissions. An integrated multi-point
sample of the stack gas will be taken concurrently with each modified Method 5 APFO sampling run. The
integrated gas sample will either be analyzed for oxygen and carbon dioxide content in accordance with
the procedures provided in EPA Method 3 or 3A found in 40 CFR Part 60 Appendix A. The team leader
may assume the dry molecular weight of ambient air for ambient sources, confirmed by the use of a field
portable oxygen analyzer, and forgo the collection of the integrated gas sample.
19
4.3.2 Multi-Point, Integrated Sampling Procedure.
4.3.2.1 Unless otherwise specified in an applicable regulation, or by the Admini strator, a
minimum of eight traverse points shall be used for circular stacks having diameters less than 0.61 m (24
in.), a minimum of nine shall be used for rectangular stacks having equivalent diameters less than 0.61 m
(24 in.) , and a minimum of 12 traverse points shall be used for all other cases. The traverse points shall be
located according to EPA Method I.
4.3.2.2 Evacuate the flexible bag. Connect the probe, and place it in the stack, with the tip of the
probe positioned at the sampling point. Purge the sampling line. Next, connect the bag, and make sure
that all connections are tight.
4.3.2.3 Sample Collection. Sample a slip stream at a constant rate from the exhaust of the
modified EPA Method 5 APFO sample train(± 10 percent). The sampling run should be simultaneous
with, and for the same total length of time as, the APFO emission rate determination. Collection of at
least 28 liters ( 1.0 ft3) of sample gas is recommended; however, smaller volumes may be collected, if
desired.
4.3.2.4 Obtain one integrated flue gas sample during each pollutant emission rate determination.
Within 8 hours after the sample is taken, analyze it for percent CO2 and percent 02 using either an Orsat
analyzer or instrumental analyzers.
4.3.3 Integrated Sample Analysis using Orsat Analyzer. Use an Orsat analyzer to measure 01 and CO2
concentration for dry molecular weight determination, using procedures as specified in the analyzer user's
manual. If an Orsat analyzer is used, it is recommended that the Orsat leak-check, described in Section
4.3.3.1, be performed before this determination; however, the check is optional. Calculate the dry
molecular weight as indicated in Section 4.3 .5. Repeat the analysis and calculation procedures until the
individual dry molecular weights for any three analyses differ from their mean by no more than 0.3 gi g
mole (0.3 lb/lb-mole). Average these three molecular weights, and report the results to the nearest 0.1 gig
mole (0.1 lb/lb-mole).
4.3.3.1 Leak-Check Procedure for Orsat Analyzer. Moving an Orsat analyzer frequently causes it
to leak. Therefore, an Orsat analyzer should be thoroughly leak-checked on site before the flue gas sampl e
is introduced into it. The procedure for leak-checking an Orsat analyzer is as follows :
4.3.3.2 Bring the liquid level in each pipette up to the reference mark on the capillary tubing, and
then close the pipette stopcock.
20
4.3.3.3 Raise the leveling bulb sufficiently to bring the confining liquid meniscus onto the
graduated portion of the burette, and then close the manifold stopcock.
4.3.3.4 Record the meniscus position.
4.3.3.5 Observe the meniscus in the burette and the liquid level in the pipette for movement over
the next 4 minutes.
4.3.3.6 For the Orsat analyzer to pass the leak-check, two conditions must be met:
4.3.3.7 The liquid level in each pipette must not fall below the bottom of the capillary tubing
during this 4-minute interval.
4.3.3.8
interval.
4.3.3.9
The meniscus in the burette must not change by more than 0.2 ml during this 4-minute
If the analyzer fails the leak-check procedure, check all rubber connections and stopcocks
to determine whether they might be the cause of the leak. Disassemble, clean, and regrease any leaking
stopcocks. Replace leaking rubber connections. After the analyzer is reassembled, repeat the leak-check
procedure.
4.3.4 Integrated Sample Analysis using Instrumental Analyzers
4.3.4.1 This is a modification of EPA Method 3A ( 40 CFR Part 60 Appendix A) for the analysis
of an integrated gas sample (Tedlar Bags), where Method 3A is written for the continuous analysis of a
sample gas stream over the duration of each sample run, and can be utilized at the discretion of the team
leader. The dry stack gas wi ll be analyzed with a Servomex 1440 oxygen and carbon dioxide analyzers
calibrated to EPA Method 3A/7E specifications. Ambient air may be used for the oxygen span gas upper
value. CEMS grade nitrogen will be used to zero instrumentation. All other calibration gases used wi ll be
EPA Protocol certified gases.
4.3.4.2 Measurement System Preparation, Analyzer Calibration Error, Follow Sections 8.2
through 8.5 of EPA Method 7Eto calibrate the analyzers directly with appropriate ranges of calibration
gases Record instrument information, date, operator and calibration information on Modified EPA
Method 3A form. Calibration will consist of a zero gas (CEM grade nitrogen, upper span gas and mid
range gas. Zero instruments with nitrogen, set span to accurately read upper span gas , then introduce mid
gas. All results of the linearization must be within 2% of span (range) of target concentration.
21
4.3.4.3 Connect integrated bag sample to analyzer inlet and record to the tenth of a percent the
stable values on Modified 3A data form for oxygen and carbon dioxide. One stable reading per integrated
bag.
4.3.4.4 Zero and Calibration Drift Test. Follow Section 8.5 of EPA Method 7E.Once all samples
have been analyzed and recorded, repeat the analyzer linearization calibration error without adjustments
to determine if analyzer drift has occurred. Drift of no more than 3% of span value will be accepted.
Given the relatively short duration of time from initial linearization to final calibration this is not expected
to be a concern.
4.3.4.5 Emission Calculation. Measured concentrations of oxygen and carbon dioxide will be
corrected for any calibration error or drift bias using the pre and post analysis analyzer calibration values
for zero and upscale gas that is closest to the stack value.
4.3.4.5.1 For all CO2 analyzers, and for 02 analyzers that can be calibrated with zero gas,
express all concentrations as percent.
4.3.4.5.2 For 02 analyzers that use a low-level calibration gas in place of a zero gas,
calculate the effluent gas concentration using the following equation.
Where:
Cma - Coa Cgas = ---- (Cavg - cm) + cma
Cm-Co
Cgas = Effluent gas concentration, dry basis, percent.
Cma = Actual concentration of the upscale calibration gas, percent.
Coa = Actual concentration of the low-level calibration gas, percent.
Cm = Average of initial and final analyzer calibration bias check responses for the upscale
calibration gas, percent.
Co = Average of initial and final analyzer calibration bias check responses for the low
level gas, percent.
Cavg = Average gas concentration indicated by the gas analyzer, dry basi s, percent.
4.3.5 Calculations and Data Analysis.
4.3.5.1 Nomenclature.
Mct = Dry molecular weight, gig-mole (lb/lb-mole).
22
%CO2 = Percent CO2 by volume, dry basis.
%02 = Percent 02 by volume, dry basis.
%CO = Percent CO by volume, dry basis.
%N2 = Percent N2 by volume, dry basis.
0.280 = Molecular weight of N2 or CO, divided by 100.
0.320 = Molecular weight of 02 divided by 100.
0.440 = Molecular weight of CO2 divided by 100.
4.3.5.2 Nitrogen, Carbon Monoxide Concentration . Determine the percentage of the gas that is
N2 and CO by subtracting the sum of the percent CO2 and percent 0 2 from 100 percent.
4.3.5.3 Dry Molecular Weight. Use the equation 3-1 of EPA Method 3, provided below, to
calculate the dry molecular weight of the stack gas.
Eq . 3-1
4.4 Determination of Moisture Content in Stack Gases
EPA Method 4 (40 CFR Part 60 Appendix A) procedures will be utilized to determine the stack gas
moisture content concurrent with each modified Method 5 APFO sampling run. The team leader can use
the alternative determination of moisture content using wet- bulb/dry-bulb temperature measurements as
an initialization parameter for the modified Method 5 APFO sampling method.
4.4.1 Preparation of Sampling Train
4.4.1 .1 Place known volumes of reagents in the impingers as described in Section 4.5,
Determination of APFO Emissions from Stationary Sources. Weigh and record the weight of the
desiccant impinger to the nearest 0.5 g.
4.4.1.2 Set up the sampling train as shown in Figure 4-1 of EPA Method 4 and specified in
Section 4.5. Turn on the probe heater and (if applicable) the filter heating system to temperatures of
approximately 120°C (248°F), to prevent water condensation ahead of the condenser system. Allow time
for the temperatures to stabilize. Pl ace crushed ice and water in the ice bath container.
4.4.1.3 Metering System. Same as that described in Section 4.5 .
23
4.4.1.4 Leak check: Plug the nozzle and pull a 380 mm (15 in. ) Hg vacuum. A leakage rate in
excess of 4 percent of the average sampling rate or 0 .00057 m3/min (0.020 cfm), whichever is less, is
unacceptable. Following the leak check, reconnect the probe to the sampling train.
4.4.1.5 Sampling Train Operation. During the sampling run , mai ntain an isokinetic sampling rate
consistent with the method for the Determination of APFO Emissions from Stationary Sources. For each
run , record the data required on a data sheet. Be sure to record the dry gas meter reading at the beginning
and end of each sampling time increment and whenever sampling is halted. Take other appropriate
readings at each sample point at least once during each time increment.
4.4.1.6 To begin sampling, position the probe tip at the first traverse point. Immediately start the
pump, and adjust the flow to the desired rate. Traverse the cross section, sampling at each traverse point
for an equal length of time. Add more ice and, if necessary, salt to maintain a temperature of less than 20
~C (68 °F) at the desiccant impinger outlet.
4.4.1.7 After collecting the sample, conduct a leak check of the sampling train as described in
Section 4.4.1.4. Record the leak rate. If the leakage rate exceeds the allowable rate, either reject the
results or correct the sample volume as in Section 12.3 of EPA Method 5.
4.4.2 Quality Control
Section Quality Control Measure Effect
Section 4.4.1.5 Leak rate of the sampling system Ensures the accuracy of the cannot exceed 4 percent of the volume of gas sampled (Reference average sampling rate or 0.00057 Method). m3/min (0.020 elm).
Section 4.4.1.7 Leak rate of the sampling system Ensures the accuracy of the cannot exceed 2 percent of the volume of gas sampled average sampling rate . (Approximation Method).
4.4.3 Calibration and Standardization.
NOTE: Maintain a laboratory log of all calibrations.
4.4.3.1
4.5.10.2.
Calibrate the metering system, temperature sensors, and barometer according to Sections
24
4.4.4 Analytical Procedure.
4.4.4.1 Measure the volume of the moisture condensed in each of the impingers to the nearest ml.
Determine the increase in weight of the desiccant plus impinger to the nearest 0.5 g. Record this
information and calculate the moisture content, as described in Section 4.4.5.
4.4.5 Data Analysis and Calculations.
Carry out the following calculations, retaining at least one extra significant figure beyond that of the
acquired data. Round off figures after final calculation.
4.4.5.1 Nomenclature
Bws = Proportion of water vapor, by volume, in the gas stream.
Mw = Molecular weight of water, 18.0 gig-mole ( 18.0 lb/lb-mole).
Pm = Absolute pressure (for this method, same as barometric pressure) at the dry gas meter, mm Hg (in . Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 (mm Hg)(m3)/(g-mole)(K) for metric units
Tm = T,1d = Y r = V; = Ym = Ym{std) =
Y wc(std) =
Ywsg(std) =
W r = W ; = y = Ym =
Pw =
and 21.85 (in. Hg)(ft3)/(lb-mole)(R) for English units.
Absolute temperature at meter, °K (0 R) .
Standard absolute temperature, 293 °K (528 °R) .
Final volume of condenser water, ml .
Initial volume, if any, of condenser water, ml.
Dry gas volume measured by dry gas meter, dcm (def).
Dry gas volume measured by the dry gas meter, corrected to standard conditions, dscm (dscf) .
Volume of water vapor condensed, corrected to standard conditions, scm (scf).
Volume of water vapor collected in silica gel, corrected to standard conditions, scm (scf).
Final weight of si li ca gel or silica gel plus impinger, g.
Initial weight of silica gel or silica gel plus impinger, g.
Dry gas meter calibration factor.
Incremental dry gas volume measured by dry gas meter at each traverse point, dcm (def).
Density of water, 0 .9982 g/ml (0.002201 lb/ml).
25
4.4.5.2 Volume of Water Vapor Condensed
Where:
~1•c(std) Vf-Vi Ps R(T)std
(Pttd MW
Vwc(std) =K1 (V1 - 11;)
K 1 = 0.001333 m3/ml for metric units,
= 0.04706 ft3/ml for Engli sh units.
4.4.5.3 Volume of Water Collected in Silica Gel.
where:
V = (wF -1Yi)RTstd V =K (W - W) \l'.rg (std) M K wsg (std) 3 F i
Pstd w 2
K2 = 1.0 gig for metric units
= 453.6 g/lb for Engli sh units
K3 = 0.001335 m3/g for metric units,
= 0.04715 ft3/g for English units .
4.4.5.4 Sample Gas Volume
where:
Vm(std)
K4 = 0.3855 °K/mm Hg for metric units,
= 17.64 °R/in. Hg for English units.
NOTE: If the post-sample leak rate (Section 4.4.1.7) exceeds the allowable rate, correct the value of Vm
in Equation 4-3, as described in Section 12.3 of Method 5.
26
4.4.5.5 Moisture Content
~vc(std) + V.~:sg(std) Bws =-----------
~vc(std) + V.I:sg(std) + V,n(std)
4.4.5.6 In saturated or moisture droplet-laden gas streams, two calculations of the moisture
content of the stack gas shall be made, one using a value based upon the saturated conditions (see EPA
Method 4 Section 4.1 ), and another based upon the results of the impinger analysis. The lower of these
two values of Bws shall be considered correct.
4.5 Determination of APFO Emissions from Stationary Sources
4.5.1 Presampling Preparation
It is suggested that sampling equipment be maintained according to the procedures described in APTD-
0576. The determination of APFO emissions from a stationary source includes the performance of three
replicate sample runs conducted consecutively.
4.5.1.1 Place 200 to 300 g of desiccant in each of several air-tight containers. Weigh each
container, including desiccant, to the nearest 0.5 g, and record this weight. As an alternative, the desiccant
need not be preweighed, but may be weighed directly in its impinger or sampling holder just prior to train
assembly.
4.5.1.2 Check filters visually against light for irregularities, flaws, or pinhole leaks. Label filters
of the proper diameter on the back side near the edge using numbering machine ink. As an alternative,
label the shipping containers (glass petri dishes), and keep each filter in its identified container at all times
except during sampling.
4.5.2 Preliminary Determinations.
4.5.2.1 Select the sampling site and the minimum number of sampling points according to
Section 4.5.2.2 Determine the stack pressure, temperature, and the range of velocity heads using Method
2; Determine the moisture content using Section 4.4. Determine the stack gas dry molecular weight, as
described in Section 4.3.
4.5.2.2 Select a nozzle size based on the range of velocity heads, such that it is not necessary to
change the nozzle size in order to maintain isokinetic sampling rates . During the run , do not change the
27
nozzle size. Ensure that the proper differential pressure gauge is chosen for the range of velocity heads
encountered (see Section 8.3 of EPA Method 2).
4.5.2.3 Select a suitable probe liner and probe length such that all traverse points can be sampled.
For large stacks , consider sampling from opposite sides of the stack to reduce the required probe length.
4.5.2.4 Select a total sampling time greater than or equal to the minimum total sampling time
specified in the procedures for the specific industry such that (I) the sampling time per point is not less
than 2 minutes (or some greater time interval as specified by the Administrator), and (2) the sample
volume taken (corrected to standard conditions) will exceed the required minimum total gas sample
volume. The latter is based on an approximate average sampling rate. It is anticipated that APFO sample
runs will be conducted over a 2-hour time period with a designed test volume between 60 and 90 dry
standard cubic feet. The team leader is responsible for setting the test time and air sample volume for each
test location.
4.5.2.5 The sampling time at each point shall be the same. It is recommended that the number of
minutes sampled at each point be an integer or an integer plus one-half minute, in order to avoid
timekeeping errors.
4.5.3 Preparation of Sampling Train
4.5.3.1 During preparation and assembly of the sampling train , keep all openings where
contamination can occur covered until just prior to assembly or until sampling is about to begin. Place
I 00 ml of deionized water in the first impinger, place 100 ml of 0.1 N NaOI-1 in the second impinger, place
100 ml of 0.0lN Na2B4O1 buffer solution in the third impinger, add a preweighed desiccant impinger as
the fourth impinger of the sample train.
4.5.3.2 Using a tweezer or clean disposable surgical gloves, place a labeled (identified) filter in
the filter holder. Be sure that the filter is properly centered and the gasket properly placed so as to prevent
the sample gas stream from circumventing the filter. Check the filter for tears after assembly is
completed. Place the filter holder between last impinger and the silica gel impinge.
4.5.3.3 When glass probe liners are used, install the selected nozzle using a silicone 0- ring when
stack temperatures are less than 260 °C (500 °F) or a heat-resistant graphite ferrule when temperatures are
higher. When metal liners are used, install the nozzle as discussed above or by a leak-free direct
mechanical connection. Mark the probe with heat resistant tape or by some other method to denote the
proper distance into the stack or duct for each sampling point.
28
4.5.3.4 Using a tweezer or clean disposable surgical gloves, place a labeled glass fiber filter
(identified) in the filter holder to be placed in the oven. Be sure that the filter is properly centered and the
gasket properly placed so as to prevent the sample gas stream from circumventing the filter. The filter
support must be of non- fluoropolymer construction i.e silicone gasket glass frit. Check the filter for tears
after assembly is completed.
4.5.3.5 Attach to the oven filter outlet a coiled condenser in horizontal position to the top of
XAD2 trap oriented vertically on top of a knock out impinger. The connection from the coiled condenser
to the XAD2 trap should have a thermocouple in the gas stream to measure XAD2 trap temperature or
exit of condenser. Alternatively, if necessary, tape a thermocouple to the exterior of the trap inlet and
insulate well. Cover XAD2 trap to minimize light exposure. Connect submergible pump with tubing to
deliver cooling water from the ice bath to the coiled condenser and jacketed XAD2 trap. This may be
done in series with the coolest water entering the XAD2 trap bottom and exiting the coiled condenser at
the inlet side.
4.5.3.6 Set up the train as shown in Figure 5-1 of EPA Method 5, using a Silicone 0-ring to
achieve each ground glass joint seal.
4.5.3.7 Place crushed ice around the impingers.
4.5.4 Leak-Check Procedures.
4.5.4.1 Leak Check of Metering System Shown in Figure 5-1 of EPA Method 5. That portion of
the sampling train from the pump to the orifice meter should be leak-checked prior to initial use and after
each shipment. Leakage after the pump will result in less volume being recorded than is actually sampled.
The following procedure is suggested (see Figure 5-2): Close the main valve on the meter box. Insert a
one-hole rubber stopper with rubber tubing attached into the orifice exhaust pipe. Disconnect and vent the
low side of the orifice manometer. Close off the low side orifice tap. Pressurize the system to 13 to 18 cm
(5 to 7 in.) water column by blowing into the rubber tubing. Pinch off the tubing, and observe the
manometer for one minute. A loss of pressure on the manometer indicates a leak in the meter box; leaks,
if present, must be corrected .
4.5.4.2 Pretest Leak Check. A pretest leak check of the sampling train is recommended, but not
required. If the pretest leak check is conducted, the following procedure should be used.
4.5.4.3 After the sampling train has been assembled, turn on and set the probe heating systems to
the desired operating temperatures. Allow time for the temperatures to stabilize. If a Viton A 0-ring or
29
other leak-free connection is used in assembling the probe nozzle to the probe liner, leak-check the train
at the sampling site by plugging the nozzle and pulling a 380 mm ( 15 in. ) Hg vacuum. Leakage rates in
excess of 4 percent of the average sampling rate or 0.00057 m3/min (0.020 cfm), whichever is less , are
unacceptable.
NOTE: A lower vacuum may be used , provided that it is not exceeded during the test.
4.5.4.4 The following leak-check instructions for the sampling train described in APTD- 0576
and APTD-0581 may be helpful. Start the pump with the bypass valve fully open and the coarse adjust
valve completely closed. Partially open the coarse adjust valve, and slowly close the bypass valve until
the desired vacuum is reached. Do not reverse the direction of the bypass valve, as this will cause water to
back up into the filter holder. If the desired vacuum is exceeded, either leak-check at this higher vacuum,
or end the leak check and start over.
4.5.4.5 When the leak check is completed, first slowly remove the plug from the inlet to the
probe and immediately turn off the vacuum pump. This prevents the water in the impingers from being
forced backward into the filter holder and the desiccant from being entrained backward into the third
impinge.
4.5.4.6 Leak Checks During Sample Run . If, during the sampling run , a component (e.g. , filter
assembly or impinger) change becomes necessary, a leak check shall be conducted immediately before
the change is made. The leak check shall be done according to the procedure outlined in Section 4.5.4.3
above, except that it shall be done at a vacuum equal to or greater than the maximum value recorded up to
that point in the sample run. If the leakage rate is found to be no greater than 0.00057 m3/min (0.020 cfm)
or 4 percent of the average sampling rate (whichever is less), the results are acceptable, and no correction
will need to be applied to the total volume of dry gas metered; if, however, a higher leakage rate is
obtained, either record the leakage rate and plan to correct the sample volume as shown in Section 12.3 of
this EPA Method 5, or void the sample run.
NOTE: Immediately after component changes, leak checks are optional. If such leak checks are
done, the procedure outlined in Section 4.5.4.3 above should be used.
4.5.4.7 Post-Sample Leak Check. A leak check of the sampling train is mandatory at the
conclusion of each sampling run. The leak check shall be performed in accordance with the procedures
outlined in Section 4 .5.4.3 , except that it shall be conducted at a vacuum equal to or greater than the
maximum value reached during the sampling run. If the leakage rate is found to be no greater than
30
0.00057 m3/min (0.020 cfm) or 4 percent of the average sampling rate (whichever is less), the results are
acceptable, and no correction need be applied to the total volume of dry gas metered. If, however, a
higher leakage rate is obtained, either record the leakage rate and correct the sample volume as shown in
Section 12.3 of EPA Method 5, or void the sampling run.
4.5.5 Sampling Train Operation.
During the sampling run, maintain an isokinetic sampling rate (within IO percent of true isokinetic unless
otherwise specified by the Administrator) and a temperature in the sample probe of 120 ± 14 °C (248 ± 25
°F), or such other temperature as specified by an applicable subpart of the standards or approved by the
Administrator. The sample filter is maintained at ambient temperature.
4.5.5.1 For each run , record the data required on a data sheet such as the one shown in Figure 5-3
of EPA Method 5. Be sure to record the initial DGM reading. Record the DGM readings at the beginning
and end of each sampling time increment, when changes in flow rates are made, before and after each
leak check, and when sampling is halted. Take other readings indicated by Figure 5-3 at least once at each
sample point during each time increment and additional readings when significant changes (20 percent
variation in velocity head readings) necessitate additional adjustments in tlow rate. Level and zero the
manometer. Because the manometer level and zero may drift due to vibrations and temperature changes,
make periodic checks during the traverse.
4.5.5.2 Clean the portholes prior to the sample run to minimize the chance of collecting
deposited material. To begin sampling, verify that the probe heating system is up to temperature, remove
the nozzle cap, verify that the pitot tube and probe are properly positioned. Position the nozzle at the first
traverse point with the tip pointing directly into the gas stream. Immediately start the pump, and adjust the
tlow to isokinetic conditions. Nomographs are available which aid in the rapid adjustment of the
isokinetic sampling rate without excessive computations. These nomographs are designed for use when
the Type S pitot tube coefficient (Cp) is 0.85 ± 0.02, and the stack gas equivalent density ldry molecular
weight (Md)] is equal to 29 ± 4. APTD-0576 details the procedure for using the nomographs. A
spreadsheet designed for EPA Method 5 calculations is the preferred means of calculating and adjusting
the isokinetic sample rate.
4.5.5.3 When the stack is under significant negative pressure (i .e., height of impinger stem), take
care to close the coarse adjust valve before inserting the probe into the stack to prevent water from
backing into the filter holder. If necessary, the pump may be turned on with the coarse adjust valve
closed.
31
4.5.5.4 When the probe is in position, block off the openings around the probe and porthole to
prevent unrepresentative dilution of the gas stream.
4.5.5.5 Traverse the stack cross-section, as required by Method I or as specified by the
Administrator, being careful not to bump the probe nozzle into the stack walls when sampling near the
walls or when removing or inserting the probe through the portholes; this minimizes the chance of
extracting deposited material.
4.5.5.6 During the sample run, make periodic adjustments to keep the temperature of the sample
probe at the proper level; add more ice and, if necessary, salt to maintain a temperature of less than 20°C
(68°F) at the desiccant impinger outlet. Also, periodically check the level and zero of the manometer.
4.5.5.7 If the pressure drop across the filter becomes too high, making isokinetic sampling
difficult to maintain, the filter may be replaced in the midst of the sample run. It is recommended that
another complete filter assembly be used rather than attempting to change the filter itself. Before a new
filter assembly is installed, conduct a leak check (see Section 4.5.4.3 ). The total APFO weight shall
include the summation of the filter assembly catches.
4.5.5.8 A single train shall be used for the entire sample run, except in cases where simultaneous
sampling is required in two or more separate ducts or at two or more different locations within the same
duct, or in cases where equipment failure necessitates a change of trains. In all other situations, the use of
two or more trains will be subject to the approval of the Administrator.
NOTE: When two or more trains are used, separate analyses of the front-half and (if applicable)
impinger catches from each train shall be performed, unless identical nozzle sizes were used on all trains,
in which case, the front-half catches from the individual trains may be combined (as may the impinger
catches) and one analysis of front-half catch and one analysis of impinger catch may be performed.
Consult with the Administrator for details concerning the calculation of results when two or more trains
are used.
4.5.5.9 At the end of the sample run, close the coarse adjust valve, remove the probe and nozzle
from the stack, turn off the pump, record the final DGM meter reading, and conduct a post-sample leak
check, as outlined in Section 4.5.4.3. Also, leak-check the pitot lines as described in EPA Method 2,
Section 8.1 . The lines must pass this leak check, in order to validate the velocity head data.
32
4.5.6 Calculation of Percent lsokinetic.
Calculate percent isokinetic to determine whether the run was valid or another sample run should be
made. If there was difficulty in maintaining isokinetic rates because of source conditions, consult with the
Administrator for possible variance on the isokinetic rates.
4.5.7 Sample Recovery.
4.5.7.1 Proper cleanup procedure begins as soon as the probe is removed from the stack at the
end of the sampling period. Allow the probe to cool.
4.5.7.2 When the probe can be safely handled, wipe off all external PM near the tip of the probe
nozzle, and place a cap over it to prevent losing or gaining PM. Do not cap off the probe tip tightly while
the sampling train is cooling down. This would create a vacuum in the filter holder, thereby drawing
water from the impingers into the filter holder.
4.5.7.3 Before moving the sample train to the cleanup site, remove the probe from the sample
train and cap the open outlet of the probe. Be careful not to lose any condensate that might be present.
Remove the umbilical cord from the last impinger, and cap the impinger.
Disconnect the oven filter assembly, coiled condenser, XAD2 trap. If liquid is present in coiled
condensor attempt to drain into trap before disconnecting. Cap all openings as di sconnecting from the
sample train . Either ground-glass stoppers, plastic caps, rubber stoppers or Para film may be used to close
these openings.
4.5.7.4 Transfer the probe oven filter assembly, coiled condenser, XAD2 trap and impinger
assemblies to the cleanup area. This area should be clean and protected from the wind so that the chances
of contaminating or losing the sample will be minimized.
4.5.7.5 Save a portion of the methanol used for cleanup as a blank. Take 200 ml of thi s methanol
directly from the wash bottle being used, and place it in a polyethylene sample container labeled
"methanol blank."
4.5.7.6 Inspect the train prior to and during disassembly, and note any abnormal conditions.
Treat the samples as follows:
4.5.7.6.1 Container No. 1. Carefully remove the oven filter from the filter holder, and
place it in an identified petri dish container or other container provided by the analytical laboratory.
33
Use a pair of tweezers and/or clean disposable surgical gloves to handle the filter. If it is necessary
to fold the filter, do so such that the PM cake is inside the fold. Using a dry Nylon bristle brush
and/or a sharp-edged blade, carefully transfer to the petri dish any PM and/or filter fibers that
adhere to the filter holder gasket.
4.5.7.6.2 Container No. 2. Taking care to see that dust on the outside of the probe or other
exterior surfaces does not get into the sample, quantitatively recover PM or any condensate from
the probe nozzle, probe fitting, probe liner, and filter glassware by washing these components with
methanol and placing the wash in a polyethylene sample container. Deionized water may be used
instead of methanol at the discretion of the team leader if it is found to be a more effective recovery
solvent. In these cases, save a water blank.
Perform the sample recovery as follows:
4.5.7.6.2.1 Carefully remove the probe nozzle. Clean the inside surface by rinsing with
methanol from a wash bottle and brushing with a Nylon bristle brush. Brush until the
methanol rinse shows no visible particles, after which make a final rinse of the inside surface
with methanol. Dry the sample nozzle with acetone prior to the next sample run and at the
completion of sampling at each location.
4.5.7.6.2.2 Rinse the probe liner with methanol by tilting and rotating the probe while
squirting methanol into its upper end so that all inside surfaces will be wetted with methanol.
Let the methanol drain from the lower end into an Erlenmeyer flask fitted with a ground glass
socket attached to and compatible with the probe liner ball joint. Follow the methanol rinse
with a probe brush. Hold the probe in an inclined position, squirt methanol into the upper end
as the probe brush is being pushed with a twisting action through the probe; catching any
methanol and particulate matter that is brushed from the probe. Run the brush through the
probe three times or more until no visible PM is carried out with the methanol or until none
remains in the probe liner on visual inspection. With stainless steel or other metal probes, run
the brush through in the above prescribed manner at least six times since metal probes have
small crevices in which particulate matter can be entrapped. Rinse the brush with methanol,
and quantitatively collect these washings in the sample container. After the brushing, make a
final methanol rinse of the probe. Rinse the probe with acetone to aid drying prior to use in the
next sample run and at the end of sampling at each location.
34
4.5.7.6.2.3 Clean the inside of the front half and back half of the oven filter holder and
connecting glassware by rubbing the surfaces with a Nylon bristle brush if needed to remove
visible particulate and rinsing with methanol. Rinse each surface three times or more if needed
to remove visible particulate. Make a final rinse of the brush (if used) and filter holder.
Carefully rinse out the back half of the filter holder also.
4.5.7.6.3
Container No. 2.
4.5.7.6.4
Coiled condenser. Rinse the coiled condenser three times with methanol into
XAD2 trap. Seal both ends of the XAD2 trap and label for lab submittal.
4.5.7.6.5 Impinger Contents. Treat the impingers as follows: Make a notation of any color
or film in the liquid catch. Measure the liquid by the volumetric method or by the mass method.
Method 5 allows for either approach. The volumetric method includes measuring the volumes of
the XAD2 knockout impinger and the following three impingers individually with polyethylene
graduated cylinders dedicated to each impinger reagent type to within I ml. Record the volume of
liquid present. The mass method includes measuring the net change in mass of the
knockout/impinger or the sample bottle. The mass method will be used whenever practical because
it involves less sample transfers and fewer chances for cross contamination. The volume in each
impinger is required to calculate the moisture content of the effluent gas. The contents of the
knockout impinger (below XAD2 trap) is transfeITed to a polyethylene sample container (Container
No. 3) labeled "deionized water". The contents of the first impinger after the knockout impinger is
also transferred to the polyethylene sample container (Container No. 3) labeled "deionized water".
Rinse the knockout and first impinger three times with methanol from a wash bottle and add the
methanol wash to Container No. 2. Transfer the contents of the second impinger after the knockout
to a polyethylene sample container (Container No. 4) labeled "0. lN NaOH". Rinse the impinger
three times with methanol from a wash bottle and add the methanol wash to Container No. 2.
Transfer the contents of the third impinger to a polyethylene sample container (Container No. 5)
labeled "0.0IN Buffer Solution". Rinse the impinger three times with methanol from a wash bottle
and add the methanol wash to Container No. 2.
4.5.7.6.6 Container No. 6. Carefully remove the final filter (after last impinger) from the
filter holder, and place it in an identified petri dish container or other container provided by the
analytical laboratory. Use a pair of tweezers and/or clean disposable surgica l gloves to handle the
filter. Using a dry Nylon bristle brush and/or a sharp-edged blade, carefully transfer to the petri
dish any PM and/or filter fibers that adhere to the filter holder gasket. Clean the inside of the front
35
half and back half of the filter holder and connecting glassware by rubbing the su1faces with a
Nylon bristle brush if needed to remove visible particulate and rinsing with methanol. Rinse each
surface three times or more if needed to remove visible particulate. Make a final rinse of the brush
(if used) and filter holder. Place the methanol rinses into container No. 2. After all methanol
washings and particulate matter have been collected in the sample containers, tighten the lids on
the all sample containers so that methanol will not leak out when it is shipped to the laboratory.
Mark the height of the fluid levels to allow determination of whether leakage occurred during
transport. Label the container to identify clearly its contents.
4.5.8 Sample Transport.
Whenever possible , containers should be shipped in such a way that they remain upright at all times.
Samples to be stored and transported cooled
4.5.9 Quality Control.
Quality Control Measure Effect
Sampling equipment leak check and Ensures accurate measurement of calibration. stack gas flow rate, sample volume.
4.5.1 O Calibration and Standardization.
NOTE: Maintain a laboratory log of all calibrations.
4.5.10.1 Probe Nozzle. Probe nozzles shall be calibrated before their initial use in the field . Using
a micrometer, measure the ID of the nozzle to the nearest 0.025 mm (0.001 in.). Make three separate
measurements using different diameters each time, and obtain the average of the measurements. The
difference between the high and low numbers shall not exceed 0.1 mm (0.004 in.). When nozzles become
nicked, dented, or corroded, they shall be reshaped, sharpened, and recalibrated before use.
4.5.10.2 Pitot Tube. Pi tot tubes will be calibrated annually using the geometric criteria for design
of "S" Type pitot tubes . Pitot tubes meeting the criteria will be assigned the coefficient of 0.84. Pitots
tubes not meeting the criteria will be repaired to meet criteria or discarded. Prior to each test the pitot
should be inspected for damage or misshapen openings.
4.5.10.3 Metering System.
4.5.10.3.1 Calibration Prior to Use. Before its initial use in the field, the metering system
shall be calibrated as follows: Connect the metering system inlet to the outlet of a wet test meter
36
that is accurate to within 1 percent. The wet test meter should have a capacity of 30 liters/rev ( 1
ft3/rev). A spirometer of 400 liters (14 ft3) or more capacity, or equivalent, may be used for this
calibration, although a wet test meter is usually more practical. The wet test meter should be
periodically calibrated with a spirometer or a liquid displacement meter to ensure the accuracy of
the wet test meter. Spirometers or wet test meters of other sizes may be used, provided that the
specified accuracies of the procedure are maintained. Run the metering system pump for about I 5
minutes with the orifice manometer indicating a median reading as expected in field use to allow
the pump to warm up and to permit the interior surface of the wet test meter to be thoroughly
wetted. Then, at each of a minimum of three orifice manometer settings, pass an exact quantity of
gas through the wet test meter and note the gas volume indicated by the DGM. Also note the
barometric pressure and the temperatures of the wet test meter, the inlet of the DGM, and the outlet
of the DGM. Select the highest and lowest orifice settings to bracket the expected field operating
range of the orifice. Use a minimum volume of 0.14 m3 (5 ft3) at all orifice settings. Record all the
data on a form similar to Figure 5-5 of EPA Method 5 field and calculate Y, the DGM calibration
factor, and H@, the orifice calibration factor, at each orifice setting as shown on Figure 5-5 .
Allowable tolerances for individual Y and H@ values are given in Figure 5-5. Use the average of
the Y values in the calculations in Section 4.5.
4.5.10.3.1.1 Before calibrating the metering system, a leak check should be conducted. For
metering systems having diaphragm pumps, the normal leak-check procedure will not detect
leakages within the pump. For these cases the following leak- check procedure is suggested:
make a 10-minute calibration run at 0.00057 m3/min (0.020 cfm). At the end of the run , take
the difference of the measured wet test meter and DGM volumes. Divide the difference by 10
to get the leak rate. The leak rate should not exceed 0.00057 m3/min (0.020 cfm).
4.5.10.3.2 Calibration After Use. After each field use, the calibration of the metering
system shall be checked by performing three calibration runs at a single, intermediate orifice
setting (based on the previous field sampling runs), with the vacuum set at the maximum value
reached during the sample run series. To adjust the vacuum, insert a valve between the wet test
meter and the inlet of the metering system. Calculate the average value of the DGM calibration
factor. If the value has changed by more than 5 percent, recalibrate the meter over the full range of
orifice settings, as detailed in Section 4.5.10.2.1. The Alternate procedure described in EPA
Method 5 may also be used if approved by Administrator.
37
4.5.10.3.3 Acceptable Variation in Calibration. If the DGM coefficient values obtained
before and after a sample run series differ by more than 5 percent, the sample run series shall either
be voided, or calculations for the sample run series shall be performed using whichever meter
coefficient value (i.e., before or after) gives the lower value of total sample volume.
4.5.10.4 Probe Heater Calibration. Use a heat source to generate air heated to selected
temperatures that approximate those expected to occur in the sources to be sampled. Pass this air through
the probe at a typical sample flow rate while measuring the probe inlet and outlet temperatures at various
probe heater settings. For each air temperature generated, construct a graph of probe heating system
setting versus probe outlet temperature. The procedure outlined in APTD-0576 can also be used. Probes
constructed according to APTD- 0581 need not be calibrated if the calibration curves in APTD-0576 are
used. Also, probes with outlet temperature monitoring capabilities do not require calibration.
NOTE: The probe heating system shall be calibrated before its initial use in the field.
4.5.10.5 Temperature Sensors. Use the procedure in Section I 0.3 of EPA Method 2 to calibrate
in-stack temperature sensors. Dial thermometers, such as are used for the DGM and condenser outlet,
shall be calibrated against mercury-in-glass thermometers.
4.5.10.6 Barometer. Calibrate against a mercury barometer.
4.5.11 Analytical Procedure.
All analytical samples will be sent to an off-site analytical laboratory for analysis.
4.5.12 Data Analysis and Calculations.
Carry out calculations, retaining at least one extra significant figure beyond that of the acquired data.
Round off figures after the final calculation. Other forms of the equations may be used, provided that they
give equivalent results.
4.5.12.1 Nomenclature.
An
Bws
cAPFO
EAPFO
I
=
=
=
=
=
Cross-sectional area of nozzle, m2 (ft2).
Water vapor in the gas stream, proportion by volume.
Concentration of APFO in stack gas, dry basis, corrected to standard conditions, lb/dscf.
Mass emission rate of APFO, lb/hr
Percent of isokinetic sampling.
38
mAPFO = Total amount of APFO collected, lb.
Mw = Molecular weight of water, 18.0 gig-mole ( 18.0 lb/lb-mole) .
Pbar = Barometric pressure at the sampling site, mm Hg (in. Hg)
Ps = Absolute stack gas pressure, mm Hg (in. Hg).
Pstd = Standard absolute pressure, 760 mm Hg (29.92 in. Hg).
R = Ideal gas constant, 0.06236 [(mm Hg)(m3)]/[(K)(g-mole)] (2 1.85 [(in . Hg)(ft3)] / [(0 R)(lb-mole)]}.
Tm = Absolute average DGM temperature (see Figure 5-3), K (0 R).
Ts = Absol ute average stack gas temperature (see Figure 5-3), K (0 R).
Tstd = Standard absolute temperature, 293 K (528 °R).
Vic = Total volume of liquid collected in impingers and silica gel (see Figure 5-6), ml.
Vm = Volume of gas sample as measured by dry gas meter, dcm (def).
Vm(std) = Volume of gas sample measured by the dry gas meter, corrected to standard conditions, dscm ( dscf) .
Vw(std) = Volume of water vapor in the gas sample, corrected to standard conditions, scm (scf).
vs = Stack gas velocity, calculated by Method 2, Equation 2-7, using data obtained from Method 5, m/sec (ft/sec).
Qd = Stack gas volumetric flow rate, DSCFM
y = Dry gas meter calibration factor.
.t.H = Average pressure differential across the orifice meter (see Figure 5-4 ), mm H20 (in. H20) .
e = Total sampling time, mi n.
dp = Sampling time interval , from the final (nth) component change unti l the end of the sampling run, min.
13.6 = Specific gravity of mercury.
60 = Sec/min.
100 = Conversion to percent.
4.5.12.2 Average Dry Gas Meter Temperature and Average Orifice Pressure Drop. See data
sheet (EPA Method 5 Figure 5-3) .
4.5.12.3 Dry Gas Volume. Correct the sample volume measured by the dry gas meter to standard
conditions (20 °C, 760 mm Hg or 68 °F, 29.92 in. Hg) by using the fo llowing equation:
39
where:
( /ili) /ili T.,d P1,ar +-- Pbar +--v )Vy 13.6 =K-V y 13.6
m(std m TP rm T m ~ m
Kl = 0.3858 °K/mm Hg for metric units,
= 17 .64 °R/in. Hg for English units .
4.5.12.4 Volume of Water Vapor Condensed.
where:
K2 = 0.001333 m3/ml for metric units,
= 0.04706 ft3/ml for English units.
K1 Vi.,
4.5.12.5 Moisture Content.
V,i·(std) B,i·s =-------
Vm(str1) + ~~(std)
NOTE: In saturated or water droplet-laden gas streams, two calculations of the moisture content of
the stack gas shall be made, one from the impinger analysis (equation above), and a second from the
assumption of saturated conditions. The lower of the two values of Bws shall be considered correct. The
procedure for determining the moisture content based upon the assumption of saturated conditions is
given in Section 4.0 of EPA Method 4. For the purposes of this method, the average stack gas temperature
from each sampling run may be used to make this determination, provided that the accuracy of the in
stack temperature sensor is ± 1 °C (2°F).
4.5.12.6 Total APFO Mass. Determine the total collected APFO from the sum of the APFO
mass obtained from the analysis of the contents sample containers I through 5.
40
4.5.12.7 APFO Concentration.
CAPFO = mAPFo / Vm(std)
4.5.12.8 lsokinetic Variation.
where:
v,,, y ( Afl) lOOT, K 4 V,c -- P1,ar +--Tm 13.6
I+--~---------0 v. P., A,,
K4 = 0.003454 [(mm Hg)(m3)]/[(ml) (°K)] for metric units ,
= 0.002669 [(in. Hg)(ft3)]/[(ml)(0 R)] for English units.
4.5.12.9 Acceptable Results. If 90 %:S I :S 110 %, the results are acceptable.
4.5.12.10 Stack Gas Velocity and Volumetric Flow Rate. Calculate the average stack gas velocity
and volumetric flow rate, if needed, using data obtained in this method and the equations in Sections 12.3
and 12.4 of EPA Method 2.
4.5.12.11 APFO Mass Emission Rate
EAPFO = CAPFO X Qd X 60
41
.Sampling Legend
6 .Heated Air Sample
D .Liquid Waste Sample
• .Solid Waste Sample
.Tote /Recyde)
/ .R1nseate Waste
.to POTW
•
.Transfer Pump
i FeedRoll
Figure 1 - Typical Glass Cloth Process Diagram
Vent to Atmosphere
i 6 .g-------------~::i-------------------~ I I I
Feed .Tank
I I I I I Drying and ·---~ 1 Baking Tower I I I I I
Filter ltO---- , __ .,
/ Waste Filter to
.Landfill
•
Dip Pan
/ .Rinseate Waste to POTW
•
42
.Trim Waste
Collect for .Landfill Disposal
•
.Take-Up Roll
Figure 2 - Typical Cast Film Process Diagram
.Sampling Legend
~ .Hot Air Sample
D Liquid Waste Sample
.Feedstock Tote (Recycled) --Tote~
Rinseateto POTW
•
.1bstrate eed Roll
I Vent to Atmosphere
I 6,
r----------------~
Prying .and
.Sintering Tower
Heat .Supply
------{>
Pip Pan (Manually filled dip pans)
l Rinseate Waste to POTW
•
43
Product .Film
Take-up Roll
.Substrate Take-up
Roll
f 25"
SAINT GOBAIN PERFORMANCE PLASTICS MERRIMACK, NEW HAMPSHIRE
0
i
AIR DILUTION FAN
17.75" DIA STACK
2 TEST PORTS @ 90'
ROOF LINE
>8 DIA I t I I I
I
I
INSIDE BUILDING
FIGURE 3
TEST PORT LOCATIONS MA TOWER EXHAUST
44
FROM MA TOWER
NOT TO SCALE
SAINT GOBAIN PERFORMANCE PLASTICS MERRIMACK, NEW HAMPSHIRE
t 31"
0
i
>8 DIA I f I
I
I
I
I
AIR DILUTION FAN
2 TEST PORTS @ 90'
INSIDE BUILDING
FIGURE 4
TEST PORT LOCATIONS MS TOWER EXHAUST
45
ROOF LINE
FROM MS TOWER
NOT TO SCALE
DAMPER
QX CAST FILM PROCESS
SAINT GOBAIN PERFORMANCE PLASTICS MERRIMACK, NEW HAMPSHIRE
ROOF LINE
---- 7 II~ EXTERIOR r WALL
14.0"
I
I I
I
f J. 7 I
16' >2.0 DIA I
PROPOSED OUTLET PORTS
PROPOSED INLET PORTS
Lo~ I >0.5 DIA I...------
FIGURE 5
PILOT CONTROL
DEVICE
TEST PORT LOCATIONS QX CAST FILM INLET/OUTLET
46
14.0"
---i r I >0.5 DIA
oi >2.0 DIA
tj FAN ROOF LINE
--'-----'- - - -
NOT TO SCALE
iillll SCOTT-MARRIN, INC. PGVP Vendor ID: H12012
6531 Box Springs Blvd • Riverside, CA 92507-0725 Phone: +1(951)653-6780 • Fax: +1(951)653-2430 • www.scottmarrin .com
Report Of Analysis EPA Protocol Gas Mixtures
BARR01 TO: Barr Engineering Co
Attn : Benjamin Wiltse 5150 West 76th Street Edina, MN 55439-2900 (952) 832-2885
CYLINDER NUMBER: CA03980
COMPONENT
Carbon dioxide
Oxygen
Nitrogen
CONCENTRATION (v/v) ± EPA UNCERTAINTY
4.90 ± 0.06 %
21 .23 ± 0.22 %
Balance
CERTIFICATION DATE: August 19, 2013
ppm = µmole/mole %= mole-%
REFERENCE STANDARD
GMIS SRM 1674b Samp#: 7-14-E
REPORT NO: 63595-01
REPORT DATE: August 29, 2013
CUSTOMER PO NO: BAW06112013
CYLINDER SIZE: 150A (141 std cu ft)
CYLINDER PRESSURE: 2000 psig
ANALYZER MAKE, MODEL, SIN, DETECTION
Varian Model 3400 Serial # 10680
REPLICATE ANALYSIS DATA
8/19/2013 4.90 %
Cyl#: CC116770 Cyl#: CLM006389 Thermal Conductivity 4.90 % 7.99 ± 0.08 % 6.98 ± 0.07 % Gas Chromotography 4.89 % Exp: 8/2/2019 Exp: 6/16/2012 LAST CAL DATE: 8/7/2013 x: 4.90 %
GMIS SRM 2659a Varian Model 3800 8/26/2013 Samp#: 71-0-23 Serial # None 21 .22 %
Cyl#: CC88824 Cyl#: CAL015788 Thermal Conductivity 21 .23% 24.92 ± 0.25 % 20.72 ± 0.043 % Gas Chromotography 21 .24 % Exp: 2/25/2021 Exp: 1/1/2016 LAST CAL DATE: 8/7/2013 x: 21 .23 %
EPA EXPIRATION DATE: August 20, 2021
i = EPA weighted mean The above analyses were performed in accordance with Procedure G1 of the EPA Traceability Protocol , Report Number EPA600/R-12/531 , dated May 2012.
The above analyses shou d not be used if the cylinder pressure is less than 100 psig .
ANALYST: __ ~--=--~~---"'---'---- APPROVED: ~ M.S.Calhoun / J. T. Marrin
The only liability of this company for gas which fails to comply wi th this analysis shall be replacement or reanalysis thereof by the company without extra cost.
47
RED /BALL 1 ECHNICAL GAS SERVICES
Jif PJIA
c:.aa.au.. ..........
Accreditation #62754
Red Ball Technical Gas Service 555 Craig Kennedy Way Shreveport, LA 71107
800-551 -8150 PGVP Vendor ID# G12017
EPA PROTOCOL GAS CERTIFICATE OF ANALYSIS Cylinder Number: EB0099614 Certification Date: 08/14/2017
Product ID Number: 126786 Expiration Date: 08/12/2025 Cylinder Pressure: 1900 PSIG MFG Facility: - Shreveport - LA COA# EB0099614.20170726-0 Lot Number: EB0099614.20170726
Customer PO. NO.: Tracking Number: B1908036
Customer: Previous Certification Dates:
I This calibration standard has been certified per the May 2012 EPA Traceability Protocol, Document EPA-600/R-12/531,
[
Component
Carbon Dioxide Oxygen
Nitrogen
I using procedure G 1.
Do Not Use This Cylinder Below 1oo·pslg'(0.7 Megapascal),
Concentration
Balance
9.5% 9.46%
Certified Concentration(s) Uncertainty Analytical Principle
±0.10 % ±0.05 %
NDIR
MPA
Analytical Measurement Data Available Online.
Reference Standard(s) Serla I Number Lot Expiration Type Balance Component Concentration
EB0060740
SG9916836
Component
02 CO2
Principle
MPA
NDIR
EB0060740.20170209
SG-9916836
08/05/2025
06/0612022
GMIS
NTRM
Analytical Instrumentation Make
Thermo
Thermo
Model 410i
410i
N2
N2
Serial
1162980025
1162980025
0 2
CO2
MPC Date
08/09/2017
08/14/2017
This is to certify the gases referenced have been cal ibrated/tested , and veri fied to meet the defined specifications. This calibration/test was performed using Gases or Scales that are traceable through National Institute of Standards and Technology (NIST) to the International System of Units (SI). The basis of compliance stated is a comparison of the
measurement parameters to the specified or required calibration/testing process. The expanded uncertainties use a coverage factor of k=2 to approximate the 95% confidence level of the measurement. unless otherwise noted. This calibration certificate
applies only to the item described and shall not be reproduced other than in full, without written approval from Red Ball Technical Gas Services. If not included, the uncertainty of calibrations are available upon request and were taken into account
when determining pass or fail. 48
24 %
19.98 %
Assayed On
08/14/2017
08/09/2017
Uncertainty(%)
0.502
0.7
SMART-CERT
NIST Reference
071001
101001
Brandon Theus Analytical Chemist
Assay Laboratory: Red Ball TGS Version 02-<, , Rev ised on 2017-06-29
RED /BALL TECHNICAL GAS SERVICES
Cylinder Number: EB0099613 Product ID Number: 121026 Cylinder Pressure: 1900 PSIG
CERTIFICATE OF ANALYSIS (Zeto Arnbient Nitrogen)
Certif ication Date: Expiration Date: MFG Facility:
COA# EB0099613.20170727-0 Lot Number: Customer PO. NO.: Tracking Number: Customer: Previous Certification Dates:
This mixture is for laboratorv use ontv, not for druo, household or other use.
Assay Laboratory: Red Ball TGS 555 Craig Kennedy Way Shreveport, LA 71107
800-551-8150
07127/2017 07/2512025 RBTGS-Shreveport-LA EB0099613.201 70727 B1908012
This mixture is certified In Mole % to be within ±2% of the actual number reoorted with a confidence of 95%. This mixture was manufactured bv scale; welahts traceable to N.t.S.T. Certificate #822/266926-02.
Do Not Use This Cvlinder Below 100 pslo (0.7 Meoapascall.
Composing Material: Zero Ambient Nitrogen, Cert., Sz152
Component Nitrogen Oxygen as Impurity
Carbon Dioxide as Impurity
Carbon Monoxide as Impurity
Total Oxides of Nitrogen as Impurity
Sulfur Dioxide as Impurity
Total Hydrocarbons as Impurity
Red Boll Technical Gas Service PGVP Vendor ID# 012017 Information and Ordering
800-551 -8150 Fax (318-425-6309)
f.
Specification Balance
<1.0 PPM <0.5 PPM
<0.5 PPM
<0.1 PPM
<0.1 PPM
<0.1 PPM
~ PJIA
.,._.... __ •. Accreditat ion #62754
, 49
Concentration Balance
<1.0 PPM
<0.5 PPM
<0.5 PPM
<0.1 PPM
<0.1 PPM
<0.1 PPM
Anthony Cyr Analyt ical Chemist
Version 02-B, Revised on 2015-05-27
Appendix A-6
ORD Report #1 April 4, 2018
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY JAi, •NAL F ' IIF<l L E. f H L.\E :RA~ r
RE__.EA.f-n.,HT IAN•,Lf F'll,R~ J• r-11
April 4, 2018
Mr. Clark Friese, Assistant Commissioner
,fF cc F - E E~n, I-' 1/[1 C'EVE , F MEIIT
New Hampshire Department of Environmental Services (NI I DES) 29 Hazen Drive P.O. Box 95 Concord, New Hampshire 03301
Dear Mr. Friese:
I am pleased to provide you with this initial laboratory report of pertluorocarboxylatc (PFCA) concentrations in solid samples (char and soil). This report is in response to your request of June 22, 2017 asking for laboratory assistance analyzing per- and polyfluoroalkyl substances (PFAS) in environmental samples. PFC As are a subset of PF AS. This report relates to solid matrix samples sent to our Athens Lab that included three tower char and another three soil samples. We understand that these samples were collected by New Hampshire Department of Environmental Services (NH DES), on August 23 , 2017 and September 8, 2017, respectively. These samples were received at our Athens Lab by Dr. John Washington who was also responsible for their lab processing.
It is our understanding that this infom,ation was requested by NH DES to help in their ongoing investigation into the presence of PFAS in the environment near manufacturing facilities of interest. This request relates to our research capabilities and interests applying targeted and nontargeted analysis methods for discovery of the nature and extent of PF AS environmental occurrence associated with industrial releases. The current report is limited to targeted results only. Our non-targeted work requires considerable post-processing manual effort and therefore will lag the targeted results.
EPA continues to develop analytical methods for many PF AS compounds in various media including some of those included in this report. The data enclosed provides information related to the concentration of certain PF AS in the media sampled. In this report we do not interpret exposure or risk from these values. EPA docs not currently have health based standards, toxicity factors or associated risk levels for PF J\S, other than perfluoroctanoic acid (PFOA), perfluoroocatane sulfonate (PFOS), and pertluorobutanesulfonic acid (PFBS). Therefore, while the data presented indicate the presence of PFCA, no conclusions can be made related to human or environmental exposure and risk.
Thank you for inviting us to be part of this effort that helps to further both EPA' s and New Hampshire·s understanding of an important issue in the state. This is just one of many Agency efforts that demonstrate EPA ·s commitment to cooperative federalism.
April4.2017
The results presented in lhe attachment represent the work of many within ORD"s ational Exposure Research Laboratory. Our technical experts include Ors. John Washington, Mark Strynar, Andy Lindstrom, Seth Nev.ton, Thomas Jenkins, and James McCord. Our Quality Assurance team includes Sania Tong-Argao and Brittany Stuart. Management support and coordination has been provided by Ors. Timothy Auckley. Myriam Medina-Vera. Jack Jones, Adam Biales, and Brian Schumacher.
If you have any questions or concerns, do not hesitate to contact me at (919) 541-2106 or via email at '" al ki n ·. tirn ·u i: XU.!.O \ or Tim Buckley at (9 I 9) 541-2454 or via email at huckk, .timoth v a l'. x1. 10,·. I look for.vard lo our continued work together.
Attachment
cc: Meghan Cassidy. USEPA. Region 1 Deb Szaro, USEPA, Region I Jeff Morris, USEP/\ OPPT Betsy Behl. USEPA, OW Peter Grevatt, USEPA, OW Andy Gillespie, USEPA, ORD Timothy Buckley. USEPA, ORD
~;Jud!-Timothy H. Watkins Director
April4,2017
Summary of Methods and Results
New Hampshire Department of Environmental Services (NH DES), in coordination with Region I, requested ORD's technical support in analyzing PFAS in environmental samples potentially impacted by industrial sites within the state. NH DES assumed responsibility for the collection of samples and their shipment to our laboratories. ORD was responsible for sample extraction and analysis of PF AS. We are providing the results of our analysis as they become available. This is our first report.
The current report includes results for char (n=3) and soil (n=3) samples that were sent to and analyzed under the direction of Dr. John Washington within our Athens Lab. Samples were collected in containers provided by NH DES and shipped to EPA. Thirteen PFCA analytes (Table 1) were analyzed using methods described within an approved Quality Assurance Project Plan (QAPP) 1 and that have been generally described in Rankin et al., 2015 .2 In brief, each sample was divided into three -1 g aliquots and extracted and analyzed in triplicate. Extracts were analyzed by liquid chromatography/ mass spectrometry (Waters Acquity UPLC coupled to a Waters Quattro Premier XE tandem) and quantified using mass-labeled internal standards. These analyses were perfonned on samples, process blanks, and check standards using internalcalibration curves for quantitation. The mean value of the triplicate analysis is reported. Reported results are based on the identification and quantification of analytes using certified standards (i.e. , targeted analysis).
Some of the sample extract required dilution so that concentrations were within the acceptable range of the calibration curve. The reported results have been adjusted for each dilution factor and flagged accordingly in Table 2.
Table 1. Summary of Reported Perfluorocarboxylates
. PF'CA . Compoµnd N~me .t\Crf)D,Y.~ · CAS Nu11,1ber C4 Perfluorobutanoic acid PFBA 375-22-4 C5 Perfluoropentanoic aci(.l PFPeA 2706-90-3 C6 Perfluorohexanoic acid PFI-lxA 307-24-4 C7 Perfluoroheptanoic acid PFHpA 375-85-9 cs Perfluorooctanoic acid PFOA 335-67-1 C9 Perfluorononanoic acid PFNA 375-95-1 CIO Perfluorodecanoic acid PFDA 335-76-2 Cl 1 Perfluoroundecanoic acid PFUnDA 2058-94-8 C12 Perfluorododecanoic acid PFDoDA 307-55-1 C13 Perfluorotridecanoic acid PFTrDA 72629-94-8
1 Strynar, M.; Washington, J.; Lindstrom, A. ; Henderson, W. 2017. Quality Assurance Project Plan: Non-Targeted Analyses of Per- and Polyfluoroa!kyl Substances (PF AS) for New Hampshire Department of Environmental Services (NHDES). D-EMMD-PHCB-0 15-QAPP-0l . 2 K. Rankin, S. A. Mabury, T. M. Jenkins, J. W. Washington, A North American and global survey of perfluoroalkyl substances in surface soils: Distribution patterns and mode of occurrence. Chemosphere 16 1, 333-341 (2015).
April 4, 2017
C14 Perfluorotetradecanoic acid PFTeDA 376-06-7 C16 Perfluorohexadecanoic acid PFHxDA 67905-19-5 Cl8 Perfluorooctadecanoic acid PFOcDA 16517-11-6
Targeted results are provided in Table 2 below for 13 perfluorocarboxylates that range from C4 through C 18. Results are reported in mass of PF AS per unit mass of dry solid. Please note that the units are reported in µgig for char samples and pg/g for soil samples. Precision of our measurements was estimated by the relative standard deviation (RSD) of triplicate extractions/analyses. For char across all of the compounds, the median RSD was 12.9% and ranged from 1.6% to 48.8%. Similarly for soils, the median RSD was 19.2% and ranged from 1.2 to 51.6%. The values reported for target analytes all exceeded levels detected in process blanks (p:::0.05) and were corrected for any low detections in process blanks. No field blanks were provided or analyzed; however, quality control check standards were analyzed at varying concentrations throughout the analysis to ensure that measurements at varying points of the calibration range were within quality control specifications. Recovery of these standards ranged from 79.3% to 118% which was within our ± 30% criteria for acceptability.
As was expected, the measured perfluorocarboxylates tended to occur at higher concentrations in the char samples than the soil with char results ranging from <LOO (limit of detection) to 1430 µgig. Soil results were in the pg/grange and varied from <LOD to 7420 pg/g. Among the char, PFCA concentrations were consistently higher at "QX Tower" followed by the "MS Tower." and lowest for the "MA Tower." Similarly for soil, PFCA concentrations generally trended "EPAORDS1" > "EPAORDS2" > "EPAORDS3." Across both matrices, the highest concentration was consistently observed for C8 (PFOA).
Table 2. Concentration of Perfluorocarboxylates Measured in New Hampshire Samples
. PFCA. . ... SampleiO M~~rjx Co11c. · Unjt . Fiai!is)* C4 MS Tower Char 3.13 µgig D2 cs MS Tower Char 4.41 µg/g D2 C6 MS Tower Char 15.1 ug/g D2 C7 MS Tower Char 7.60 ug/g 02 C8 MS Tower Char 439 ug/g D3 C9 MS Tower Char 4.25 µg/g D2 Cl0 MS Tower Char 9.44 µgig D2 Cl 1 MS Tower Char 4.55 µgig D2 C12 MS Tower Char 9.12 µgig D2 Cl3 MS Tower Char 5.07 µgig D2 C14 MS Tower Char 10.8 µgig D2 C16 MS Tower Char 7.95 µg/g D2 Cl8 MS Tower Char -- µg/g D2, <LOD C4 OX Tower Char 20.1 µg/g D2
cs QXTower Char 41.7 ug/g D2
C6 QXTower Char 122 ug/g D2 C7 QXTower Char 71.5 µg/g D2
April 4, 2017
·· P:FCA Sami)l~ll) . M~trix · C,9nc . . Un.it ;Flae(~)~ C8 QX Tower Char 1430 ug/g D3 C9 QX Tower Char 36.2 µgig D2
Cl0 QXTower Char 74.8 µg/g D2 Cl 1 QXTower Char 52.2 µgig 02 Cl2 QXTower Char 87.5 ug/g D2 C13 QXTower Char 62.9 µgig D2 C14 QX Tower Char 79.3 µgig D2 C16 QX Tower Char 28.4 U!l/g D2,<LOQ
Cl8 QX Tower Char 3.14 µgig D2, <LOQ
C4 MA Tower Char -- µgig D2, <LOD C5 MA Tower Char -- µgig D2,<LOD C6 MA Tower Char 0.212 µgig D2, <LOQ C7 MA Tower Char ·- µgig D2,<LOD C8 MA Tower Char 2.55 µgig D2, <LOQ
C9 MA Tower Char -- µgig O2, <LOD CIO MA Tower Char -· µg/g D2, <LOO
Cll MA Tower Char -- ug/g D2,<LOD C1 2 MA Tower Char 0.100 µgig D2, <LOQ C13 MA Tower Char 0.095 LW/g D2, <LOQ Cl4 MA Tower Char 0.193 us:dg D2 C16 MA Tower Char 0.423 µgig D2 Cl8 MA Tower Char 0.357 µgig D2,<LOQ
C4 EPAORDSl Soil 194 pg/g UD C5 EPAORDSI Soil 389 pg!g UD, <LOQ C6 EPAORDSl Soil 1270 pg/g UD C7 EPAORDSl Soil 615 pg/g UD
C8 EPAORDSl Soil 7420 pg/g Dl , <LOQ
C9 EPAORDSl Soil 240 pg/g UD ClO EPAORDSl Soil 238 og/g UD, <LOQ Cll EPAORDSl Soil 90.0 pg/g UD, <LOQ Cl2 EPAORDSl Soil -- pg/g UD,<LOD Cl3 EPAORDSl Soil -- pg/g UD, <LOD Cl4 EPAORDSI Soil -· pg/g UD, <LOD CI6 EPAORDSI Soil -- pg/g UD, <LOD C18 EPAORDSJ Soil -- pg/g UD,<LOD
C4 EPAORDS2 Soil -- pg/g UD, <LOD
cs EPAORDS2 Soil -- pg/g UD, <LOD C6 EPAORDS2 Soil 175 pg/g UD,<LOQ
C7 EPAORDS2 Soil 540 pg/g UD cs EPAORDS2 Soil 6950 pglg UD C9 EPAORDS2 Soil -- pg/g UD,<LOD
C10 EPAORDS2 Soil 34.3 pg/g UD, <LOQ
· PFCA . S3~pl~ ID Cl I EPAORDS2 C12 EPAORDS2 C13 EPAORDS2 Cl4 EPAORDS2 C16 EPAORDS2 C18 EPAORDS2
C4 EPAORDS3 cs EPAORDS3 C6 EPAORDS3 C7 EPAORDS3 cs EPAORDS3 C9 EPAORDS3
CIO EPAORDS3 Cll EPAORDS3
C12 EPAORDS3 C13 EPAORDS3 Cl4 EPAORDS3 C16 EPAORDS3 C18 EPAORDS3
* Flags defined: UD = undiluted D1 = 10-fold dilution D2 = 104-fold dilution D3 = 105-fold dilution
M3 tti,x Soil Soil Soil Soil Soil Soil
Soil Soil Soil Soil Soil Soil Soil Soil Soil Soil Soil Soil Soil
April 4, 2017
Co,.ic . Unit FJag(s)* -- pQ/g UD,<LOD
-- pg/g UD, <LOD
-- pg/g UD,<LOD -- pg/g UD,<LOD
-- pg/g UD,<LOD -- pg/g UD, <LOD
-- pg/g UD,<LOD 18.9 pg/g UD,<LOQ 56.1 pg/g UD,<LOQ 165 pg/g UD,<LOQ
1140 pg/g UD 21.4 pg/g UD,<LOQ 19.4 pg/g UD,<LOQ 5.70 pg/g UD,<LOQ
-- ovg UD, <LOD
-- pg/g UD, <LOD
-- pg/g UD,<LOD
-- pg/g UD,<LOD
-- mdg UD,<LOD
<LOQ = Less than limit of quantitation (defined as exceeding process blanks p>0.05 but :S0.001) <LOD = Less than limit of detection (defined by p:S0.05)
Appendix A-7
ORD Report #2
July 24, 2018
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY NATIONAL EY~n~URE PE ErRL H LABPRATLJP
OFFl•'E OF RESEARL.H AtlD [.•E:VEL 1PM NT RE:SEARl H TR IAN , LE ARI' NC _ --11
July 24. 2018
Mr. Clark Freise, Assistant Commissioner New Hampshire Department of Environmental Services 29 Hazen Drive PO Box 95 Concord, New Hampshire 03301
Dr. Mr. Freise,
I am pleased to provide you with the attached report which presents additional results of analyses of per - and polyfluoroalkyl substances (PF AS) concentrations in char and soil samples collected by the New Hampshire Department of Environmental Services (NH DES) staff. This report provides results of non-targeted analyses of the same three soil and three char samples that were previously analyzed for C4-C I 8 .. legacy'' perfluorocarboxylates using targeted methods and deli vercd to the NH DES in our April 4, 2018 report . The current report is significant in identifying the presence of two PF AS series that to our knowledge has not been previously reported as an environmental contaminant.
It is our understanding that this infonnation was requested by the NH DES to help in their ongoing investigation into the presence of PFAS in the environment near manufacturing facilities of interest. This request relates to our research capabilities and interests applying targeted and non-targeted analysis methods for discovery of the nature and extent of PF AS environmental occurrence.
The U.S. Environmental Protection Agency continues to develop analytical methods for many PFAS compounds in various media including some of those included in this report. The data enclosed provides information related to the concentration of certain PFAS in the media sampled. In this report we do not interpret exposure or risk from these values. The EPA does not currently have health based standards, toxicity factors or associated risk levels for PF AS, other than perfluoroctanoic acid (PFOA), pertluoroocatane sulfonatc (PFOS), and pertluorobutanesulfonic acid (PFBS). Therefore. while the data presented indicate the presence of two novel PFAS series, no conclusions can be made related to human or environmental exposure and risk .
Thank you for inviting us to be part of this effort that helps to further both the EPA' s and New Hampshire·s understanding of an important issue in the state. Providing this type of support to the NH DES aligns well with our research capabilities and interests in applying targeted and nontargeted analysis methods. It also demonstrates our commitment to. and the relevance of our research in support of~ cooperative federalism to address pressing environmental health concerns of New Hampshire residents.
If you have any questions or concerns, do not hesitate to contact me at (919) 541-2106 or via email at \\at l-. ins.tim u t: pa. gm or Tim Buckley at (919) 541-2454 or via email at hud.k , .timoth, ,u t: m. 1m . [ look forward to our continued work together.
Attachment
cc: Meghan Cassidy, USEPA. Region 1 Deb Szaro, USEP A, Region 1 Jeff Morris, USEPA OPPT Betsy BehL USEPA, OW Peter Grevatt, USEPA, OW Andy Gillespie, USEPA ORD Timothy Buckley, USEPA. ORD
~£Jr Timothy 1-1 . Watkins Director
Technical Report #2: ORD Technical Support to New Hampshire: Non-Targeted PFAS Measurements in Char and Soil
Date: July 24, 2018
Report Team
• Laboratory Chemists: Drs. John Washington, Mark Strynar, Andy Lindstrom, Seth Newton, Thomas Jenkins, and James McCord
• Quality Assurance Review: Sania Tong-Argao and Brittany Stuart • Management Coordination and Review: Ors. Myriam Medina-Vera, Jack Jones,
Adam Biales, and Brian Schumacher • Report Preparation: Dr. Tim Buckley
Summary of Methods and Results
New Hampshire Department of Environmental Services (NH DES), in coordination with Region 1, requested ORD's technical support in analyzing PFAS in environmental samples potentially impacted by industrial sites within the state. NH DES assumed responsibility for the collection of samples and their shipment to our laboratories. ORD was responsible for sample extraction and analysis. We are providing the results of our analysis as they become available. Our first report dated April 4, 2018 provided targeted analysis results for C4-C 18 "legacy" perfluorocarboxylates in 3 soil and 3 char samples.
This is our second report and it includes non-targeted analysis results conducted by Dr. John Washington of the same soil and char samples previously reported (Report No. 1). The nontargeted analysis differs from the targeted in that chemical identification and quantification does not have the benefit of being based on a known standard. Accordingly, there is more uncertainty both in terms of identification and concentration estimation.
The PF AS reported here were identified and quantified using non-targeted analysis methods described within an approved Quality Assurance Project Plan (QAPP)1
• These methods are also generally described in Rankin et al., 2015.2 In brief, each sample was divided into three - 1 g aliquots and extracted and analyzed in triplicate. Extracts were analyzed by liquid chromatography I mass spectrometry using a Waters Acquity UPLC coupled to a Waters Xevo G2-XS QTOF for non-targeted identification followed by a Waters Acquity UPLC coupled to a Waters Quattro Premier XE tandem for quantitation. The non-targeted PF AS are identified based on a combination of high-resolution mass spectral data along with patterns of fragmentation. Without the benefit of a standard, we quantify based on the fully fluorinated homologue for which we do have a standard. In effect, our quantification of the non-targeted analyte, in this
1 Strynar, M.; Washington, J.; Lindstrom, A.; Henderson, W, 2017. Quality Assurance Project Plan: Non-Targeted Analyses of Per- and Polyfluoroalkyl Substances (PF AS) for New Hampshire Department of Environmental Services (NHDES). D-EMMD-PHCB-015-QAPP-0 1. 2 K. Rankin, S. A Mabury, T. M. Jenkins, J . W. Washington, A North American and global survey of perfluoroalkyl substances in surface Soil: Distribution patterns and mode ofoccurrence. Chemosphere 161, 333-341 (2015).
July 24, 2018
case the hydrogenated carboxylic acid, assumes that the mass spectrometer responds to the fully fluorinated species as it does the hydrogenated, i.e. yielding identical chromatographic peak areas. A calibration curve is used for quantification, however, the curve is developed for chemicals for which we have a standard and that are similar to our non-targeted analyte. In most cases, the standard is the fully fluorinated version of the PF AS we are quantifying as noted in Table 3. Our experience with these chemicals has shown that this means of estimation often is within an order of magnitude uncertainty. Some of the sample extracts required dilution so that concentrations were within the acceptable range of the calibration curve. The reported results have been adjusted for each dilution factor and flagged accordingly. These analyses were performed on samples and process blanks using internal-calibration curves for quantitation. The mean value of the triplicate analysis is reported.
Measurement precision was estimated by the relative standard deviation (RSD) from triplicate analysis of each sample. For char samples, the median RSD across all of the compounds was 4.4% and ranged from 0. 7% to 31 %. We observed greater variability in soil where concentrations were much lower. The median RSD for soil was 66% and ranged from 8.4% to 170%. Field blanks were not provided so limits of detection (LOD) and quantification (LOQ) were detennined from process blanks at p~0.05 and p:S0.001, respectively. Reported concentrations were corrected for any low detections in process blanks.
The non-targeted analysis identified two PF AS series not previously reported to our knowledge as an environmental contaminant. The first is a PF AS carboxylic acid series that ranges from C6 to C20 where there is a single hydrogen substitution for fluorine. Our identification of the chemicals in this series is provided in Table 1. We are confident in chemical identities based on mass-spectral data including high resolution mass and fragmentation data. However, at present we cannot determine the exact location of the hydrogen substitution, and therefore we have not specified a CAS number. The generic hydrogenated poly fluorinated carboxylic acid (HPFCA) structure is given in Figure 1 with the hydrogen arbitrarily placed in the terminal position.
H F 0
F F OH n
Figure 1. Generic structure of hydrogenated polyfluorinated
carboxylic acid (HPFCA). At present, the exact position of the hydrogen is
undetermined.
2
July 24, 2018
Table l. PFAS Single Hydrogen Substituted Carboxylic Acid Series Identified Using Non-Tar2cted Analyses that are the Sub,iect of this Report.
Carbon Anion No. Compound Name Acronym Formula
HC6 Hydro-polvfluorohexanoic acid HPFHxA HC6F10O2
BC7 Hvdro-polvfluoroheptanoic acid HPFHpA HC1F12O2
HC8 Hydro-polyfluorooctanoic acid HPFOA HCsf14O2
HC9 Hydro-polyfluorononanoic acid HPFNA HC9f16O2
HCI0 Hydro-polyfluorodecanoic acid HPFDA HC10F1sO2
HCl 1 Hvdro-polvfluoroundecanoic acid HPFUA HC11F20O2
HC12 Hydro-polyfluorododecanoic acid HPFDoA I-IC12F22O2
HC13 Hydro-polyfluorotridecanoic acid HPFTrA HC13F24O2
HC14 Hvdro-polyfluorotetradecanoic acid HPFTeA HC14F26O2
HC15 Hydro-polyfluoropentadecanoic acid HPFPDA HC1sF2sO2
HC16 Hydro-polyfluorohexadecanoic acid HPFHxDA HC16F30O2
HC17 Hvdro-polyfluoroheptadecanoic acid HPFHpDA HC11F32O2
HC18 Hvdro-oolvfluorooctadecanoic acid HPFODA HC1sf34O2
HC19 I-lydro-polyfluorononadecanoic acid HPFNDA HC19f36O2
HC20 Hydro-polyfluoroi~osanoic acid HPFIA HC2of3sO2
The second series discovered is a polyfluorinated sulfonic acid series, again with a single hydrogen substitution (Table 2). The generic hydrogenated polyfluorinated sulfonic acid (HPFSA) structure is given in Figure 2 with the hydrogen arbitrarily placed in the terminal position.
~ -H F 0
II F S - OH
II F F 0
- - n Figure 2. The generic structure of
hydrogenated polyfluorinated sulfonic acid (HPFSA). At present,
the exact position of the hydrogen is undetermined.
3
July 24, 2018
Table 2. PF AS Single Hydrogen Substituted Sulfonic Acid Series Identified Using Non-Targeted Analyses that are the Subject of this Report. Carbon Anion No. Compound Name Acronym Formula
HSC4 Hydro-polyfluorobutanesulfonate HPFBS HC4FsSO3
HSC5 Hvdro-polvfluorooentanesulfonate HPFPS HCsF10SO3
HSC6 Hydro-polytluorohexanesulfonate HPFHxS HC6F12SO3
HSC7 Hydro-polyfluoroheptanesulfonate HPFt-IpS HC1F1.iSO3
HSC8 Hydro-polyfluorooctanesulfonate HPFOS HCsF1<,SO3
HSC9 Hydro-polyfluorononanesulfonate HPFNS HC9f1gSO3
HSClO Hydro-pol vfl uorodecanesulfonate HPFDS HC10F20SO3
HSCI 1 Hydro-polyfluoroundecanesulfonate HPFUS HC11Fi2SO3
HSC12 Hvdro-polyfluorododecanesulfonate HPFDoS HC12f24SQ3
HSC13 Hydro-polyfluorotridecanesulfonate HPFTrS HCnF26SOJ
HSCI4 Hydro-polyfluorotetradecanesulfonate HPFTeS HC14F2sSO3
HSC15 Hvdro-polvfluoropentadecanesulfonate HPFPDS HC1sF30SO3
HSC16 Hydro-polyfluorohexadecanesulfonate HPFHxDS HC16F32SO3
HSC17 Hydro-polyfluoroheptadeqnesulfonate HPFHpDS HC11f34SQ3
HSC18 Hvdro-polvfluorooctadecanesulfonate HPFODS HC1sF36SO3
As was observed for perfluorocarboxylates in our first report, the hydrogen substituted analogues tended to occur at higher concentrations in char relative to soil samples. The stack char concentrations ofHPFCA ranged from <LOD (limit of detection) to 140 µgig (HC10). (Note, the upper range is uncertain because some values are only specified as exceeding the calibration range.) Among the char samples, "NHCharMA" levels generally exceeding levels observed for char from "MS" or "QX" stack samples.
Soil concentrations were orders of magnitude lower than char samples. As a result, we report soil levels in pg/g instead of µgig.The observed variation ranges from <LOD to 157 pg/g. As was observed for PFCA in our first report, concentrations of the hydrogenated substituted PFCA tended to be much higher in soil sample "S l" relative to "S2" or "S3." Having identified these novel PF AS in char and soil, we will also be looking for these same novel PF AS in water and air samples to be included in later reports.
At this time we provide concentration estimates for only HPFCA because we observed higher concentrations of the HPFCA series relative to HPFSA. Based on a comparison of peak areas between the carbon equivalents in the two series, HPFCA levels in char exceeded HPFSA by a factor of 2 to 50 except for C6 and C8 where HP FSA was greater by a factor of 10 and 1.2, respectively (results not provided). We would not expect to find HPFSA in soil at appreciable
4
July 24, 2018
levels because char PF AS concentrations generally exceed soil, and levels of HPFSA were generally low in char. As mentioned above, the concentrations reported below in Table 3 are considered semi-quantitative, likely within an order of magnitude of the actual value.
Table 3. Concentration Estimates of Single Hydrogen Substituted PFAS Carboxylic Acids from Non-Targeted Analysis.
Carbon No.* Sample ID Matrix Cone. Unit Flae:(s)** HC6 NHCharMS Char 2.98 ug/g DI HC7 NHCharMS Char 0.63 l ug/g Dl HCS NHCharMS Char 4.79 µg/g DI HC9 NHCharMS Char 10.6 µg/f!. DI HClO NHCharMS Char 9.32 Uf!h. DI HCI 1 NHCharMS Char 2.64 ug/g DI HCl2 NHCharMS Char 7.95 ug/g D1 HC13 NHCharMS Char 2.99 uf!/g DI HC14 NHCharMS Char 10.8 ug/g DI HC15 as Cl4 NHCharMS Char 5.75 ug/g DI HC16 NHCharMS Char 16.1 uiz/g D1 HCl 7 as C16 NHCharMS Char 4.02 urr/g DI HCI8 NHCharMS Char 6.30 µg/g DI HC19asC18 NHCharMS Char l.24 µgig Dl, <LOQ HC20 as C20 NHCharMS Char 0.392 µg/g Dl ,<LOQ HC6 NHCharQX Char -- µgig DI, <LOD
HC7 NHCharQX Char 0. 142 ~Lg/g DJ , <LOO HC8 NHCharQX Char -- ug/g Dl, <LOD HC9 NHCharQX Char l.71 ug/g Dl ,<LOQ HClO NHCharQX Char -- ug/g DI , <LOO HCl 1 NHCharQX Char 0.620 ug/g D1 I-IC12 NHCharQX Char -- u!!/g D1,<LOD HC13 NHCharQX Char 0.547 µg/g D1,<LOQ HC14 NHCharQX Char 0.592 µ.g/~ Dl,<LOQ HC15 as C14 NHCharQX Char 0.885 µ.g/g 01 HCI6 NHCharQX Char 0.379 udg DJ, <LOQ HCl 7 as C16 NHCharQX Char 0.220 µgig Dl,<LOQ HCl& NHCharQX Char 0.213 µg/g 01 , El HCI9 as Cl8 NHCharQX Char -- µg/g DI, <LOD HC20 as Cl8 NHCharQX Char ·- urr/g DI, <LOO HC6 NHCharMA Char 36.4 ug/g D1 HC7 NHCharMA Char 8.66 u~g DI HC8 NHCharMA Char 67.7 µgig DI HC9 NHCharMA Char 101 µgig D1 HCIO NHCharMA Char 140 ug/g DJ HCll NHCharMA Char 26.6 ug/g DI HC12 NHCharMA Char > 43.3 UI!/,:?; DI, E2 HCl3 NHCharMA Char 22.5 u!!.lg DJ HC14 NHCharMA Char > 43.3 ug/g Dl,E2 HC15 NHCharMA Char 42.9 ug/g DI
5
July 24, 2018
Table 3. Concentration Estimates of Single Hydrogen Substituted PF AS Carboxylic Acids from Non-Targeted Analysis.
CarbonNQ.* Sample ID Matrix Cone. Unit Fla2(s)** HC16 NHCharMA Char > 21.8 µg/g Dl , E2 HC17 NHCharMA Char 31.7 µg/g DI HC18 NHCharMA Char > 21.8 µg/g Dl , E2 HC19 NHCharMA Char 1.37 ug/g DI HC20 NHCharMA Char 0.356 µg/g Dl, <LOO HC6 NHEPAORD-S 1 Soil 50.9 pg/g UD, <LOO HC7 NHEPAORD-S 1 Soil 3.1 1 pg/g UD, <LOQ HC8 NHEPAORD-S I Soil 50.9 nr!lg UD HC9 NHEPAORD-Sl Soil 113 og/g UD, <LOO HCl0 NHEPAORD-S l Soii 122 pg/g UD HCll NHEPAORD-Sl Soil 28.3 pg/g UD HC12 NHEPAORD-S l Soil 104 pg/g UD HC13 NHEPAORD-S l Soil 23.8 Dlllf!. UD HC14 NHEPAORD-S l Soii 157 ori./g UD HC15 as C14 NHEPAORD-S l Soil 33.9 of!.!g UD HC16 NHEPAORD-S 1 Soil 142 pg/g UD HC17 as Cl6 NHEPAORD-S 1 Soil 8.95 pg/g UD,<LOQ HC18 NHEPAORD-Sl Soil 13.6 pg/g UD, <LOQ HC19 as Cl8 NHEPAORD-S l Soil -- pg/g UD,<LOD HC20 as C18 NHEPAORD-Sl Soil -- pg/g UD,<LOD HC6 NHEPAORD-S2 Soil -- pg/g UD, <LOD HC7 NHEPAORD-S2 Soil -- n!!/g UD, <LOD HC8 NHEPAORD-S2 Soil -- og/g UD,<LOD HC9 NHEPAORD-S2 Soil -- . pg/g UD, <LOD HCIO NHEPAORD-S2 Soil -- o!!./g UD,<LOD HCI 1 NHEPAORD-S2 Soil -- o!!/f!. UD, <LOD HC12 NHEPAORD-S2 Soil -- orr/g UD,<LOD HCl3 NHEPAORD-S2 Soil -- pg/g UD,<LOD HCI4 NHEPAORD-S2 Soil -- p_g/g UD,<LOD HC15 as Cl4 NHEPAORD-S2 Soil -- pg/g UD, <LOO HC16 NHEPAORD-S2 Soil -· pg/g UD,<LOD HC17 as Cl6 NHEPAORD-S2 Soil -- pg/g UD, <LOO HCJ8 NHEPAORD-S2 Soil -- og/g UD,<LOD HC19 as Cl8 NHEPAORD-S2 Soil -- of!/g UD,<LOD HC20 asC18 NHEPAORD-S2 Soil -- of!.!g UD, <LOD HC6 NHEPAORD-S3 Soil -- pg/g UD, <LOD HC7 NHEPAORD-S3 Soil -- pg/g UD,<LOD HC8 NHEPAORD-S3 Soil -- pr!)g UD,<LOD HC9 NHEPAORD-S3 Soil 14.3 of!.!g UD,<LOQ HCJO NHEPAORO-S3 Soil -- mr/g UD, <LOD HCI 1 NHEP A ORD-SJ Soil -- of!/g UD,<LOD HCl2 NHEPAORD-S3 Soil -- o!!lg UD, <LOD HCI3 NHEPAORD-S3 Soil 2.93 pg/g UD,<LOQ HC14 NHEPAORD-S3 Soil 11.2 pg/g UD,<LOQ HC15 asC14 NHEPAORD-S3 Soil -- pg/g UD,<LOD
6
July 24, 2018
Table 3. Concentration Estimates of Single Hydrogen Substituted PFAS Carboxylic Acids from Non-Targeted Analysis.
Carbon No.* Sample ID Matrix Cone. Unit Flae:(s)** HC16 NHEPAORD-S3 Soii 10.9 mrJg UD.<LOQ HC17 as Cl6 NHEPAORD-S3 Soil -- pg/g UD,<LOD HC18 NHEPAORD-S3 Soil -- pg,/g UD, <LOD HC19 as Cl 8 NHEP AORD-S3 Soil -- pg/g UD, <LOD HC20 as Cl8 NHEPAORD-S3 Soil -- pg/g UD, <LOO
*Unless specified otherwise, the hydrogen substituted PF AS was quantified based on the fully fluorinated analogue. * * Flags defined:
• UD = undiluted • D1 = 10-fold dilution • <LOQ = values are less than LOQ but exceed Limit of Detection (LOO) defined as
exceeding process blanks at P<0.05 level of significance • <LOD = Less than limit of detection and not significantly different than process blanks • E 1 = sample/analyte exceeded established precision criteria of +/- 30% • E2= the calibration range for the corresponding PFCA was exceeded so that the reported
values are greater than the highest calibration standard. The caUbration range varied by carbon length.
7
Appendix A-8
ORD Report #3 October 4, 2018
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY NATIONAL EXPOSURE RESEARCH LABORATORY
RESEARCH TRIANG LE PARK. NC 27711
October 4, 2018
Mr. Clark Freise, Assistant Commissioner New Hampshire Department of Environmental Services (NHDES) 29 Hazen Drive P.O. Box 95 Concord, New Hampshire 03301
Dear Mr. Freise:
•~·FFi, : E (, F '-'ESEARCIS A!-IC DEVEU) PMEt,T
I am pleased to provide the attached 3rd and 4th report from our ongoing collaborative technical support to NHDES assisting with concern over PF AS environmental contamination associated with manufacturing sites. These reports are in response to your request of June 22, 2017 asking for laboratory assistance analyzing per- and polyfluoroalkyl substances (PF AS) in environmental samples. The enclosed Report #3 provides results for surface and ground water samples. Report #4 provides the results of stack sampling.
It is our understanding that this information was requested by NHDES to help in your ongoing investigation into the presence of per- and polytluorinated alkyl substances (PF AS) in the environment near manufacturing facilities of interest. This request relates to our research capabilities and interests applying targeted and non-targeted analysis methods for discovery of the nature and extent of PF AS environmental occmTence that may be potentially associated with industrial releases. EPA continues to develop analytical methods for many PF AS compounds in various media including some of those included in this report. We are providing the results of our analysis as they become available.
In this rep01t, we do not interpret exposure or risk from these values. EPA does not currently have health-based standards, toxicity factors , or associated risk levels for PF AS, other than perfluorooctanoic acid (PFOA), perfluorocatane sulfonate (PFOS), and perfluorobutanesulfonic acid (PFBS). While the data provided in the attached reports indicate the presence of.PF AS in water samples, no conclusions can be made related to human or environmental exposure and risk.
Thank you for inviting us to be part of this effort that helps to further both EPA' s and New Hampshire ' s understanding of an important issue in the state. This is just one of many Agency efforts that demonstrates EPA 's commitment to cooperative federalism.
Jfyou have any questions or concerns, do not hesitate to contact me at (919) 541-2107 or via email at [email protected] or Tim Buckley at (919) 541-2454 or via email at [email protected]. I look fonvard to our continued work together.
Sincerely,
~~ Director National Exposure Research Laboratory Office of Research and Development
Enclosure
CC: Meghan Cassidy, USEPA, Region 1 Deb Szaro, USEP A, Region 1 Jeff Morris, USEPA OPPT Betsy Behl, USEPA, OW Peter Grevatt, USEPA, OW Andy Gillespie, USEPA, ORD Timothy Buckley, USEPA, ORD Cindy Senich-Mullen, USEPA, ORD
2
ORD NH Report #3 October 4, 2018
ORD Report #3: Technical Support to New Hampshire -Targeted PFAS Measurements in Water
Date: October 4, 2018
New Hampshire Department of Environmental Services (NHDES), in coordination with EPA Region 1, requested technical support from EPA' s Office of Research and Development (ORD) in analyzing PF AS in environmental samples potentially impacted by industrial sites within the state. NHDES assumed responsibility for the collection of samples and their shipment to our laboratories. ORD was responsible for sample extraction and analysis of PFAS. ORD' s analysis and suppo11 team for this repo11 are listed in Table 1.
Table 1. EPA Office of Research and Development analysis and report team.
Responsibility Personnel Laboratory chemistry Mark Strynar (team lead), James McCord, Seth Newton Quality assurance review Andy Lindstrom, Sania Tong-Ar.gao Management coordination and review Myriam Medina-Vera, Brian Schumacher, Timothy Buckley Report preparation Kate Sullivan
The current report includes results for water samples collected by NHDES on September 27, 2017 (n=25) in containers provided by ORD. Samples were sent to and analyzed under the direction of Dr. Mark Strynar at ORD ' s laboratories in Research Triangle Park, NC. ORD laboratory personnel were blind to sampling location. The PF AS analytes targeted for analysis are given in Table 2. These analytes were selected because previous NHDES reports have shown them to be of concern.
Water samples were analyzed by Liquid Chromatography Mass Spectrometry (LC-MS) according to methods described within an approved Quality Assurance Project Plan (QAPP) 1•
PF AS concentrations were determined against a standard calibration curve derived from authentic standards using a traditional targeted analysis approach.
1 National Exposure Research Laboratory, Quality Assurance Project Plan: Non-Targeted Analyses of Per- and Polyfluoroalk.1'1 Substances (PFAS) for New Hampshire Department of Environmental Services (NHDES), October 2, 2017.
Page 1 of 3
ORD NH Report #3 October 4, 2018
Table 2. PFAS Analytes Measured
Short Name Chemical Name Formula CAS no. GenX Perfluoro(2-methyl-3-oxahexanoic) acid C6HF11O3 13252-13-6 PFBA Perfluorobutanoic Acid C4HF1O2 375-22-4 PFPeA Perfluoropentanoic Acid CsHF9O2 2706-90-3 PFHxA Perfluorohexanoic Acid C6HF11O2 307-24-4 PFHpA Perfluoroheptanoic Acid C1HF1 3O2 375-85-9 PFOA Perfluorooctanoic Acid CsHF1 sO2 335-67-1 PFNA Perfluorononanoic Acid C9Hf17O2 375-95-1 PFDA Perfluorodecanoic Acid C1 0HF1 9O2 335-76-2 PFBS Perfluorobutane Sulfonate C4Hf9SO3 375-73-5
PFHxS Perfluorohexane Sulfonate C6HFuSO3 355-46-4 PFOS Perfluorooctane Sulfonate CsHF, 1SO3 1763-23-1
Results
Quality control results indicated analyses were within expected performance specifications. For GenX, we observed our standards to be within ±22% of our calibration curve over the range of 10 to 1000 ng/L. Quality Control spikes (100 and 500 ng/L) were within 12% of the target concentration. GenX was not detected in any field or laboratory blanks.
For the remaining PF AS analytes, we observed deviations from the calibration curve for lower range standards (i.e. 10, 50, and 100 ng/L) by as much as 74%, 52%, and 51.3%, respectively. For the 25 ng/L and higher standards, concentrations were within ±21.8% of the calibration curve. QC spike samples (100 and 500 ng/L) were within 32% of the target except for PDFA, which deviated by 62.6%.
Concentration results for the 25 water samples are presented in Table 3. Summary findings include:
• GenX was detected in one sample. All other samples were below the detection limit.
• Concentrations of other PF AS varied by sample and analyte. The range of concentrations for other analytes varied from less than the limit of detection to 2,200 ng/L.
• Most of the samples had measurable concentrations of one or more of the legacy PF AS, and many had measurable concentrations of multiple analytes.
• PFOA was consistently present at the highest concentration across the 25 samples. PFOS and PFBS were observed in multiple samples.
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ORD NH Report #3 October 4, 20 18
Table 3. PFAS Concentrations determined with targeted analysis in ng/L.
Sample ID GenX PFBA PFPeA PFlhA PFHpA PFOA PFNA PFDA PFBS PFHxS PFOS Sum EPAORD 001 <LOQ II . I 19.7 31.7 49.2 227 30.1 48.2 9.92 23.9 36.4 487
EPAORD 002 <LOQ - - - - - - 10.8 - - - 10.8
EPAORD 003 <LOQ - - - - - - 45.0 - - 19.6 64.6
EPAORD 004 <LOQ 35 .9 153 168 124 580 - 39.7 12.5 21.1 37.9 I. 170
EPAORD 005 <LOQ 36.5 143 155 126 578 - 113 18.5 15.0 37.6 1,120
EPAORD 006 <LOQ 160 577 7 13 679 2,270 23.3 12.6 9.79 38.2 278 4.760
EPAORD007 <LOQ - 9.82 18.5 25.8 IOI - - - - - 155
EPAORD 008 <LOQ - - - 14.6 70.3 - - - - - 84.9
EPAORD 009 <LOQ 35 .0 74.8 95.3 710 397 - - - - - 673
EPAORD 010 <LOQ 2 1.1 73 .9 109 134 497 - - 13 .6 12.3 - 861
EPAORD0l l <LOQ 73.8 286 38 1 500 1.460 - - 21.7 21.7 - 2,750
EPAORD 0 12 <LOQ 10.9 30.4 50.1 92.6 452 - - 9.55 86.4 - 732
EPAORD 0 13 <LOQ 9.88 31.9 49.8 11 6 448 - - - 88.7 - 744
EPAORD 0 14 <LOQ - - - - - - - - - - 0.0
EPAORD 0 15 <LOQ - 230 17.4 18.8 100 - - 11. 5 - - 171
EPAORD 016 35.4 - 18.7 26.6 35 .5 11 7 - - 14.2 - - 2 12
EPAORD 0 17 <LOQ - - 15 .6 28.5 180 - - 34.8 9.93 - 269
EPAORD 018 <LOQ - - - - 61.7 - - - - - 61.7
EPAORD 0 19 <LOQ - 11.8 15 .5 19.8 96.1 - - 57 .5 - - 20 1
EPAORD 020 <LOQ - - - 10.6 61.2 - - - 9.64 - 8 1. 5
EPAORD 02 1 <LOQ - - - 10.7 61.7 - - - - - 72.4
EPAORD 022 <LOQ - 18.9 30.5 5 1. l 166 - - 15.3 17.4 - 299
EPAORD 023 <LOQ 9.72 56.4 69.7 100 52 1 - - - 19. 1 - 776
EPAORD 024 <LOQ - - - 13.5 34.7 - - - - - 48.3
EPAORD90l <LOQ - - 18.1 53 .7 4 19 - - - 17.5 - 508
<LOQ = Less than limit of quantitation for GenX is IO ng/L - (dash) = Analyte not detected
Page3of3
Appendix A-9
ORD Report #4 October 4, 2018
UNITED STATES ENVIRONMENTAL PROTECTION AGENCY NATIONAL EXPOSURE RESEARCH LABORATORY
RESEARCH TRIANG LE PARK. NC 27711
October 4, 2018
Mr. Clark Freise, Assistant Commissioner New Hampshire Department of Environmental Services (NHDES) 29 Hazen Drive P.O. Box 95 Concord, New Hampshire 03301
Dear Mr. Freise:
•:•FFh,'. E OF RESEAP.Cf; Ar-If: ::JEVEU) PMEl,T
I am pleased to provide the attached 3rd and 4111 report from our ongoing collaborative technical support to NHDES assisting with concern over PF AS environmental contamination associated with manufacturing sites. These reports are in response to your request ofJune 22, 2017 asking for laboratory assistance analyzing per- and polyfluoroalkyl substances (PF AS) in environmental samples. The enclosed Report #3 provides results for surface and ground water samples. Report #4 provides the results of stack sampling.
It is our understanding that this information was requested by NHDES to help in your ongoing investigation into the presence of per- and polyfluorinated alkyl substances (PF AS) in the environment near manufacturing facilities of interest. This request relates to our research capabilities and interests applying targeted and non-targeted analysis methods for discovery of the nature and extent of PFAS environmental occurrence that may be potentially associated with industrial releases. EPA continues to develop analytical methods for many PFAS compounds in various media including some of those included in this report . We are providing the results of our analysis as they become available.
In this report, we do not interpret exposure or risk from these values. EPA does not currently have health-based standards, toxicity factors, or associated risk levels for PF AS, other than perfluorooctanoic acid (PFOA), perfluorocatane sulfonate (PFOS), and perfluorobutanesulfonic acid (PFBS). While the data provided in the attached reports indicate the presence of PF AS in water samples, no conclusions can be made related to human or environmental exposure and risk.
Thank you for inviting us to be part of this effort that helps to further both EPA's and New Hampshire ' s understanding of an important issue in the state. This is just one of many Agency efforts that demonstrates EPA 's commitment to cooperative federalism.
If you have any questions or concerns, do not hesitate to contact me at (919) 541-2107 or via email at [email protected] or Tim Buckley at (919) 541-2454 or via email at [email protected]. I look forward to our continued work together.
Sincerely,
~~ Director National Exposure Research Laboratory Office of Research and Development
Enclosure
CC: Meghan Cassidy, USEPA, Region 1 Deb Szaro, USEP A, Region l Jeff Morris, USEPA OPPT Betsy Behl, USEPA, OW Peter Grevatt, USEPA, OW Andy Gillespie, USEPA, ORD Timothy Buckley, USEPA, ORD Cindy Sonich-Mullen, USEPA, ORD
2
ORD NH Report #4 October 4, 2018
ORD Report #4: Technical Support to New Hampshire -
Initial Results of CIMS and T0-15 Measurements in Stack Emission SUMMA Canisters
Date: October 4, 2018
Report Team
• Laboratory Chemists: Theran Riedel , Ingrid George
• Quality Assurance Review: Sania Tong-Argao, Margie Vazquez, Libby Nessley and Brittany Stuart
• Management Coordination and Review: Myriam Medina-Vera, Adam Biales, Surender Kaushik, Brian Schumacher, Jacky Rosati , Richard Shores, Brian Gullett, Lara Phelps and Timothy Buckley
• Report Preparation: John Offen berg and Jeff Ryan
Summary of Methods and Results
New Hampshire Department of Environmental Services (NHDES), in coordination with US EPA Region I , requested technical support from US Environmental Protection Agency, Office of Research and Development (ORD) in analyzing per- and polyfluoroalkyl substances (PF AS) in stack emission samples from an industrial site within the state. NHDES assumed responsibility for the coordination of sample collection protocols with the industry. ORD was responsible for chemical analysis. We are hereby providing the initial results of whole air samples collected in stainless steel, electropolished ("SUMMA" polished), passivated 6-liter canisters over the period of26April2018to01 May2018.
This report includes non-targeted analysis results conducted by high resolution chemical ionization mass spectrometry (CIMS), as well as more conventional TO-15 analysis for specific, volatile organic hazardous air pollutants (HAPs) using unit mass resolution (i.e. , ' low res ' ) gas chromatography-mass spectrometry (GC-MS). This work is an initial attempt to adapt ambient SUMMA canisters to collect whole air, stack exhaust gases for laboratory analysis of PF AS by CIMS, as well as by TO-15 , and full-scan , low resolution mass spectrometry. The performance of adapting TO-15 to stack emissions is not currently known. Any use of quantitative results should acknowledge such limitations.
Due to this being the first time SUMMA canister sampling for PF AS compounds has been performed on/with stack emissions, the CIMS analyses are limited to tentative identifications, rather than quantification. After tentative identifications are confirmed, additional work will be needed to assess sample collection, transport, handling, and analysis impacts on measurements prior to the development of quantitative analyses. Additionally, non-targeted analysis differs from the more traditional , targeted analysis in that chemical identification and quantification does not have the benefit of being based on authen.tic standards. As such, one can expect greater uncertainty, both in terms of identification and concentration estimates through a non-targeted analysis. Some of the differences between the analysis methods are summarized in Table 1.
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ORD NH Report #4 October 4, 2018
The PF AS reported here were identified using non-targeted analysis methods described within an approved quality assurance project plan (QAPP) 1 and addendum2
• These non-targeted methods are also generally described in Rankin et al., 2015.3 The Chemical Ionization Mass Spectrometer (CIMS - Aerodyne Research, Inc, Billerica, MA) is a moderately high resolution, direct air inlet, high time resolution mass spectrometer,4 5 that has not previously been applied to non-targeted analysis of PF AS in air samples.
As stated, this study adapted ambient, whole-air SUMMA sampling to the plant ' s stack emissions. In brief, multiple evacuated SUMMA canisters were filled on-site to approximately 7 pounds per square inch absolute (psia), then transported to Research Triangle Park, North Carolina (RTP, NC) for analysis. Incomplete filling during sampling was performed in order to help prevent condensation of water induced by temperature changes during transport to RTP, NC. Upon receipt by ORD, each canister was pressurized to approximately 50 psia with clean air. Actual initial and final pressures were recorded in laboratory notebooks. Samples were analyzed first by chemical ionization mass spectrometry (CIMS) using iodide (I-) as the reagent gas until the pressure inside the canister reached 19 psia, at which point the canister was analyzed according to TO-I 5, with the additional targeted hydrocarbons of the Photochemical Assessment Monitoring Station list (PAMS). Canisters were then re-analyzed by a full-scan, low mass resolution gas chromatography - mass spectrometry (GC/MS) analysis. The TO-15 analysis can be understood as a targeted analysis of gas phase Hazardous Air Pollutants (HAPs). The subsequent full-scan analysis is similar to the non-targeted analysis presented above and in earlier work, yet the use of low mass resolution GC-MS work results in data that may be of insufficient quality to perform high resolution non-targeted data analysis.
The CIMS non-targeted PF AS compounds are tentatively identified based on the combination of high-resolution mass spectral data (i.e. , response vs. m/Q) , along with interpretation of spectral patterns, such as the presence, or absence, of a series of analogues with the addition of 50 ( or l 00) m/Q which is consistent with the addition of CF2 ( or C2F4) to the backbone of the
1 Strynar, M. ; Washington, J .; Lindstrom, A. ; Henderson , W. 2017. Quality Assurance Project Plan: Non-Targeted Analyses of Per- and Polytluoroalkyl Substances (PF AS) for New Hampshire Department of Environmental Services (NHDES). D-EMMD-PHCB-015-QAPP-0I.
2 Offenberg, J.H .. Addendum to Quality Assurance Project Plan : Non-Targeted Analyses of Per- and Polytluoroalkyl Substances (PFAS) for New Hampshire Department of Environmental Services (NHDES). DEMMD-PHCB-015-QAPP-0 1-01.
3 K. Rankin, S. A. Mabury, T . M. Jenkins, J . W. Washington , A North American and global survey of
pertluoroalkyl substances in surface Soi I: Distribution patterns and mode ofoccurrence. Chemosphere 16 I, 333-341 (2015).
4 Lee, B. H. ; Lopez-Hilfiker, F. D. ; Mohr, C. ; Kurten , T. ; Worsnop, D. R.; Thornton, J. A. , An Iodide-Adduct High
Resolution Time-of-Flight Chemical-Ionization Mass Spectrometer: Application to Atmospheric Inorganic and Organic Compounds. Environmental Science & Technology 2014, -18 (II), 6309-6317.
5 Lopez-Hilfiker, F. D. ; Iyer, S. ; Mohr, C. ; Lee, B. H. ; D'Ambro, E. L.; Kurten, T. ; Thornton, J. A. , Constraining the
sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts. Atmos. Meas. Tech. 2016, 9 (4), 1505-1512.
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ORD NH Report #4 October 4, 2018
molecule. Without the benefit of known authentic standards, identifications are effectively limited to library search matches, as well as agreement between estimates of molecular mass from empirical formulae , and measured m/Q by the instrument.
After CIMS analysis , samples were also analyzed by GC/MS according to TO-15 using Selective Ion Monitoring (SIM), then again by GC-MS, under the same chromatographic conditions, operating in full scan mode over a range of m/Q of 31 to 500. The addition of chromatography and higher energy ionization (70 eV Electron Impact) may allow for additional comparative analysis between the full scan GC-MS (low resolution full scan) and CIMS. Both CIMS and GCMS analyses were performed on all samples, and process blanks in an identical manner. For all following results, ions (i.e., compounds) observed across all three replicate canisters are indicated in the following tables, corresponding with the chemical analysis performed.
The CI MS-based non-targeted analysis tentatively identified twelve ( 12) PF AS compounds in the SUMMA canisters (Table 2). Some ambiguity remains in the assignment of the tentative identifications, largely due to the combination of soft (i.e. non-fragmentary) ionization with no chromatographic separation in the CIMS technique. For example, two PF AS compounds (6:2 telomer alcohol 364.10 Th, and the C7 perfluoro-carboxylic acid 364.10 Th) have nearly identical molecular weights, and are subsequently observed in the CIMS at nearl y indistinguishable m/Q. Given the resolution of the CIMS instrument (- 3000), it is not possible to definitively identify which of the two compounds is present (x:2 telomer alcohol, or the corresponding x + I pertluoro-carboxylic acid). At present we cannot determine the empirical formulae , and therefore, have not specified a ' most likely ' identification nor corresponding CAS number.
The GC-MS targeted SIM analysis of SUMMA canisters identified 27, 42 and 38 non-PF AS compounds in the samples from the MS, MA and QX towers, respectively. Compounds identified are listed in Table 3. Across all 9 SUMMA canisters representing non-controlled stack emissions (i.e. , from MS Tower, MA Tower, and QX Tower Inlet sampling), the following compounds were observed in all canisters: propylene, propane, chloromethane, isobutane, ]butene, ethanol, acrolein, acetone, iso-pentane, isopropyl alcohol, 1-pentene, isoprene, vinyl acetate, 2-butanone, 1-hexene, tetrahydrofuran, 2,4-dimethylpentane, benzene, 4-methyl-2-pentanone, toluene, and dodecane. Up to 118 gas phase compounds were observed across all nine samples using the TO-15 (plus PAMS compounds) method.
Comparison of pre- and post- control device implementation on the QX tower showed a small reduction in the number of compounds identified in all 3 of the post-control device canisters. However, this reduction cannot be interpreted regarding the effectiveness of the control device. Impacts, if any, of the control devices are best assessed through direct comparison of quantitative results.
Measured concentrations of the TO-15 (plus PAMS) compounds are given in Table 4 through Table 7. All measured concentrations are reported as parts per billion by volume (ppbV). In all four of these tables, there are several data descriptors (often called ' flags ' ) to identify a) the presence of contamination which leads to suspect quantitation, b) a compound coelution problem which leads to unreliable quantitation, c) a compound which was above the calibration range,
Page 3 of 26
ORD NH Report #4 October 4, 2018
from which an estimated value is based on highest calibration point (i.e. , presented as greater than the highest calibration point). Compounds below the method detection limit (MDL) are reported as < method quantitation limit (MQL). Reported values are blank corrected and normalized for dilution of the original sample by the addition of clean air. Table 4 presents concentrations measured in SUMMA canisters collected on the MS Tower, while Table 5 lists concentrations measured in samples collected on the MA Tower. Table 6 includes measured concentrations of compounds in the SUMMA canisters collected on both the inlet and outlet of the control device on the QX Tower. Table 7 includes results from three ambient samples as well as the single field blank canister.
Data analysis of the full-scan GC-MS analysis of these same canisters is not yet complete. The additional analyses may provide insight into the relative contributions of the x:2 fluoro-telomer alcohols, relative to the corresponding x+ 1 perfluoro-carboxylic acids. The fragmentation patterns of the more energetic ionization technique, as well as the potential for chromatographic separation of analytes, may provide multiple confirmatory results when compared with authentic standards. These evaluations, along with initial laboratory studies of the stability of select PF AS compounds in SUMMA canisters, is currently being performed by ORD in RTP, NC.
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ORD NH Report #4 October 4, 2018
Table 1. Overview of Collection and Analysis Methods used for SUMMA canister analysis. For comparison, LC-TOF MS and LC-HRMS, used in prior work, are also included.
Analysis Mass Chromatograp m/Q Identificatio Negativ Quantificatio Method Resolutio hy range n e Mass n
n Defect
CIMS Moderate! No 1-1000 r Adducts Yes No, not yet y High
Formulae o.oox only
No Fragmentatio n
TO-15 Low Yes Selected Confirmed No Yes
(unit Ion with
Monitorin Authentic mass)
g Standards
where possible
GC/MS Low Yes 31-500 Peak ID, No No
(unit Library mass) search,
Diagnostic fragments
LC-TOF High Yes e.g. PFAS Yes Yes, for many MS
0.000x I 00-1000 Library Standards
LC-HRMS (Orbitrap
)
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ORD NH Report #4 September 10, 20 18
Table 2. PFAS ions observed by C IMS analysis of SUMMA canister stack air samples collected from a New Hampshire manufac turing fac ility. Concentration va lues are expressed in arb itrary units.
**PRELIMINARY DATA ., Probable PFAS Composition
(mean signal, dilution normalized)
Can ID Sample Type Dilution
C3FH5O2 CSF3H903 C6F2H6O2 C6F9HSO Factor
C7F6H10O2 C7F11HSO C7F13H3O C8F7H5O4 C8F11H7O2 C8F13HSO C9FH7O2 C10F13H9O2
92.0274 174.050 148.033 264.019 240.058 314.016 349.997 298.007 344.027 364.013 166.043 408.039
background 1 system blank 532 21 16 17 9 9 6 3 16 39
RK9 ambient
4.6 12296 113 48 47 (inside facility)
71 45 40 29 27 332 757 35
5 ambient
6.1 5445 148 237 38 (lower roof)
108 59 38 54 29 102 407 66
794 ambient
10.4 4656 225 74 135 (upper roof)
543 181 66 so 41 348 1273 53
709 ambient?
529 (Field Blank)
17 9 16 9 5 4 7 16 59 6
755 MA tower
10.2 42844 886 1185 152 (Run 1)
611 168 102 59 56 171 5140 139
751 MA tower
10.2 57354 1145 1181 234 (Run 2)
483 244 95 117 33 230 5400 72
262 MA tower
9.1 66907 1028 452 306 (Run 3)
464 180 133 53 85 846 1603 108
68 MS tower
9.7 21290 612 476 77 (Run 1)
425 110 160 72 so 1849 2863 296
700 MS tower
9.4 32577 364 463 115 (Run 2)
558 117 82 so 74 242 6703 29
744 MS tower
9.4 37052 335 111 157 (Run 3)
407 159 53 63 76 207 3079 61
721 QX tower
10.2 37442 1200 1144 294 748 321 10213 1612 628 44901 7520 793 inlet (Run 1)
176 QX tower
9.4 32334 1521 948 280 706 272 9315 1605 430 43836 7291 945 in let (Run 2)
A378 QX tower
9.5 12112 446 535 130 715 196 313 127 78 2015 2786 217 inlet (Run 3)
321 QXtower
9.1 30660 501 457 313 430 171 4952 790 332 24015 3852 152 outlet (Run 1)
2045 QX tower
8.9 20723 1195 687 579 393 585 10556 1230 958 85658 2251 539 outlet (Run 2)
793 QXtower
8.2 52629 598 678 96 428 124 171 70 81 1914 2029 295 outlet (Run 3)
background 2 system blank 889 33 32 11 22 9 7 9 8 17 51 10
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0 RD NH Report #4 September I 0, 2018
Table 3. Compounds identified using selected ion monitoring GC/MS - Method : TO-I 5.
Summary of Compounds Present in T0-15 Samples
Yellow Highlight indicates compound detected in all 3 Runs
MS Tower MA Tower QX Tower Inlet QX Tower Outlet
T0-1S Target Compounds T0-15 Target Compounds T0-15 Target Compounds T0-15 Target Compounds
Propylene Propylene Propylene Propylene
Propane Propane Propane Propane
Dichlorodifluoromethane Dichlorodifluoromethane Dichlorodifluoromethane Dichlorodifluoromethane
Chloromethane Chloromethane Chloromethane Chloromethane
lsobutane lsobutane lsobutane lsobutane
Dich lorotetrafl u oroetha ne Dichlorotetrafluoroethane Dichlorotetrafluoroethane Dichlorotetrafluoroethane
Vinyl Chloride Vinyl Chloride Vinyl Chloride Vinyl Chloride
1-Butene 1-Butene 1-Butene 1-Butene
1,3-Butadiene 1,3-Butadiene 1,3-Butadiene 1,3-Butadiene
Butane Butane Butane Butane
trans-2-butene trans-2-butene trans-2-butene trans-2-butene
Bromomethane Bromomethane Bromomethane Bromomethane
cis-2-butene cis-2-butene cis-2-butene cis-2-butene
Chloroethane Chloroethane Chloroethane Chloroethane
Ethanol Ethanol Ethanol Ethanol
Vinyl Bromide Vinyl Bromide Vinyl Bromide Vinyl Bromide
Acetonitrile Acetonitrile Acetonitrile Acetonitrile
Acrolein Acrolein Acrolein Acrolein
Acetone Acetone Acetone Acetone
iso-Pentane iso-Pentane iso-Pentane iso-Pentane
Trichlorofluoromethane Trichlorofluoromethane Trichlorofluoromethane Trichlorofluoromethane
lsopropyl Alcohol lsopropyl Alcohol lsopropyl Alcohol lsopropyl Alcohol
1-Pentene 1-Pentene 1-Pentene 1-Pentene
Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
n-Pentane n-Pentane n-Pentane n-Pentane
lsoprene lsoprene lsoprene lsoprene
trans-2-pentene trans-2-pentene trans-2-pentene trans-2-pentene
cis-2-pentene cis-2-pentene cis-2-pentene cis-2-pentene
Tert-Butanol Tert-Butanol Tert-Butanol Tert-Butanol
1,1-Dichloroethene 1, 1-Dichloroethene 1, 1-Dichloroethene 1,1-Dichloroethene
Methylene Chloride Methylene Chloride Methylene Chloride Methylene Chloride
3-Chloro-1-Propene 3-Chloro-1-Propene 3-Chloro-1-Propene 3-Chloro-1-Propene
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ORD NH Report #4
MS Tower
T0-15 Target Compounds
1,1,2-Trichloro-1,2,2-trifluoroethane
Carbon Disulfide
2,2-Dimethylbutane
tra ns-1, 2-Dichloroethene
Cyclopentane
2,3-Dimethylbutane
1,1-Dichloroethane
Methyl-t -Butyl-Ether
Vinyl Acetate
2-Methylpentane
2-Butanone
3-Methylpentane
2-Chloroprene
1-Hexene
cis-1,2-Dichloroethene
Diisopropyl ether
Ethyl Acetate
n-Hexane
Chloroform
Tetrahydrofuran
Ethyl Tert-Butyl Ether
Methylcyclopentane
1,2-Dichloroethane
2,4-Dimethylpentane
1, 1, 1-T richloroethane
Benzene
Carbon Tetrachloride
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
Tert Amyl Methyl Ether
3-methylhexane
1,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane
Trichloroethene
lsooctane
Methyl Methacrylate
Heptane
cis-1, 3-Dichlo ropropene
4-Methy-2-Pentanone
MA Tower
T0-15 Target Compounds
1,l,2-Trichloro-1,2,2-trifluoroethane
Carbon Disulfide
2,2-Dimethylbutane
tra ns-1, 2-Dich loroethene
Cyclopentane
2,3-Dimethylbutane
1,1-Dichloroethane
Methyl-t-Butyl-Ether
Vinyl Acetate
2-Methylpentane
2-Butanone
3-Methylpenta ne
2-Chloroprene
1-Hexene
cis-1,2-Dichloroethene
Diisopropyl ether
Ethyl Acetate
n-Hexane
Chloroform
Tetra hydrofu ran
Ethyl Tert-Butyl Ether
Methylcyclopentane
1,2-Dichloroethane
2,4-Dimethylpentane
1, 1,1-T richloroetha ne
Benzene
Carbon Tetrachloride
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
Tert Amyl Methyl Ether
3-methylhexane
1,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane
Trichloroethene
lsooctane
Methyl Methacrylate
Heptane
cis-1, 3-Dichloropropene
4-Methy-2-Penta none
QX Tower Inlet
T0-15 Target Compounds
1,1,2-Trichloro-1,2,2-trifluoroethane
Carbon Disulfide
2,2-Dimethylbutane
tra ns-1,2-Dichloroethene
Cyclopentane
2,3-Dimethylbutane
1,1-Dichloroethane
Methyl-t-Butyl-Ether
Vinyl Acetate
2-Methylpentane
2-Butanone
3-Methylpentane
2-Chloroprene
1-Hexene
cis-1, 2-Dichloroethene
Diisopropyl ether
Ethyl Acetate
n-Hexane
Chloroform
Tetrahydrofuran
Ethyl Tert-Butyl Ether
Methyl cyclo penta ne
1,2-Dichloroethane
2,4-Dimethylpentane
1,1, 1-Trich loroethane
Benzene
Carbon Tetrachloride
Cyclohexane
2-Methylhexane
2,3-Dimethylpenta ne
Tert Amyl Methyl Ether
3-methylhexane
1,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane
Trichloroethene
I so octane
Methyl Methacrylate
Heptane
cis-1,3-Dich loropropene
4-Methy-2-Pentanone
Page 8 of26
September I 0, 2018
QX Tower Outlet
T0-15 Target Compounds
l ,1,2-Trichloro-1,2,2-trifluoroethane
Carbon Disulfide
2,2-Dimethylbutane
trans-1, 2-Dichloroethene
Cyclopentane
2,3-Dimethylbutane
1,1-Dichloroethane
Methyl-t -Butyl-Ether
Vinyl Acetate
2-Methylpentane
2-Butanone
3-Methylpentane
2-Chloroprene
1-Hexene
cis-1,2-Dichloroethene
Diisopropyl ether
Ethyl Acetate
n-Hexane
Chloroform
Tetrahydrofuran
Ethyl Tert-Butyl Ether
Methylcyclopentane
1,2-Dichloroethane
2,4-Dimethylpentane
1,1,1-T richloroethane
Benzene
Carbon Tetrachloride
Cyclohexane
2-Methylhexane
2,3-Dimethylpentane
Tert Amyl Methyl Ether
3-methylhexane
1,2-Dichloropropane
Bromodichloromethane
1,4-Dioxane
Trichloroethene
lsooctane
Methyl M ethacrylate
Heptane
cis-1,3-Dichloropropene
4-Methy-2-Pentanone
ORD NH Report #4
MS Tower
T0-15 Target Compounds
Methylcyclohexane
tra ns-1, 3-D ichlorop ropene
1, 1,2-Trichloroethane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
Dibromochloromethane
3-Methylheptane
1,2-Dibromoethane
Octane
Tetrachloroethene
1, 1, 1,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
m-Xylene
p-Xylene
Bromoform
Styrene
1, 1,2,2-Tetrach loroethane
o-Xylene
Nonane
Cumene
n-Propylbenzene
m-Ethyltoluene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
Tert-Butyl Benzene
1-Ethyl-4-Methyl Benzene
o-Ethyltoluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Decane
Sec-Butyl Benzene
1,2,3-Trimethylbenzene
1,2-Dichlorobenzene
o-Cymene
1,3-Diethyl benzene
1,2-Diethylbenzene
n-Butyl Benzene
Undecane
1,2,4-Trichlorobenzene
Naphthalene
MA Tower
T0-15 Target Compounds
Methylcyclohexane
trans-1, 3-Dichl oroprope ne
1, 1,2-Trichloroethane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
Dibromochloromethane
3-Methylhepta ne
1,2-Dibromoethane
Octane
Tetrachloroethene
1, 1, 1,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
m-Xylene
p-Xylene
Bromoform
Styrene
1, 1,2,2-Tetrachloroethane
o-Xylene
Nonane
Cumene
n-Propylbenze ne
m-Ethyltoluene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
Tert-Butyl Benzene
1-Ethyl-4-Methyl Benzene
o-Ethyltoluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Decane
Sec-Butyl Benzene
1,2,3-Trimethylbenzene
1,2-Dichlorobenzene
o-Cymene
1,3-Diethylbenzene
1,2-Diethylbenzene
n-Butyl Benzene
Undecane
1,2,4-Trichlorobenzene
Naphthalene
QX Tower Inlet
T0-15 Target Compounds
Methylcyclohexane
tra ns-1,3-Dich loropropene
1,1,2-Trichloroethane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
Dibromochloromethane
3-Methylheptane
1,2-Dibromoethane
Octane
Tetrachloroethene
1, 1, 1,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
m-Xylene
p-Xylene
Bromoform
Styrene
1, 1,2,2-Tetrachloroethane
o-Xylene
Nonane
Cumene
n-Propylbenzene
m-Ethyltoluene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
Tert-Butyl Benzene
1-Ethyl-4-Methyl Benzene
o-Ethyltoluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Decane
Sec-Butyl Benzene
1,2,3-Trimethylbenzene
1,2-Dichlorobenzene
o-Cymene
1,3-Diethylbenzene
1,2-Diethylbenzene
n-Butyl Benzene
Undecane
1, 2,4-T richlorobenzene
Naphthalene
Page 9 of 26
September I 0, 2018
QX Tower Outlet
T0-15 Target Compounds
Methylcyclohexane
tra ns-1,3-Dichloroprope ne
1,1,2-Trichloroethane
2,3,4-Trimethylpentane
Toluene
2-Methylheptane
Dibromochloromethane
3-Methylheptane
1,2-Dibromoethane
Octane
Tetrachloroethene
1, 1, 1,2-Tetrachloroethane
Chlorobenzene
Ethyl benzene
m-Xylene
p-Xylene
Bromoform
Styrene
1, 1,2,2-Tetrachloroethane
o-Xylene
Nonane
Cumene
n-Propylbenzene
m-Ethyltoluene
1,3,5-Trimethylbenzene
1,2,4-Trimethylbenzene
Tert-Butyl Benzene
1-Ethyl-4-Methyl Benzene
o-Ethyltoluene
1,3-Dichlorobenzene
1,4-Dichlorobenzene
n-Decane
Sec-Butyl Benzene
1,2,3-Trimethylbenzene
1,2-Dichlorobenzene
o-Cymene
1,3-Diethylbenzene
1,2-Diethylbenzene
n-Butyl Benzene
Undecane
1, 2,4-T richlorobenzene
Naphthalene
ORD NH Report #4
MS Tower
T0-15 Target Compounds
Dodecane
Hexach lorobutad iene
MA Tower
T0-15 Target Compounds
Dodecane
Hexachlorobutadiene
QX Tower Inlet
T0-15 Target Compounds
Dodecane
Hexachlorobutadiene
Page 10 of26
September I 0, 2018
QX Tower Outlet
T0-15 Target Compounds
Dodecane
Hexachlorobutadiene
ORD NH Report #4 September 10, 201 8
Table 4. Measured concentrations of TO- 15 (plus PAMS) compounds in MS Tower SUMMA canisters.
MS Tower
Can ID 368 700 744
Location MS Tower MS Tower MS Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/27/2018 4/ 27/2018
Data Descriptors
• Contamination present. Quantitation suspect.
• Compound coelution problem . Quantitation not reliable.
• Above calibration range. Estimated value based on highest calibration point.
• Compounds below 3 x MDL are reported as '< MQL'
• Reported values are blank corrected
Target Compounds
Propylene
Propane
Dichlorodifluoromethane
Chloromethane
lsobutane
Dich lorotet rafluoroet ha n e
Vinyl Chloride
1-Butene
1,3-Butadiene
Butane
trans-2-butene
Bromomethane
cis-2-butene
Chloroethane
Ethanol
Vinyl Brom ide
Acetonit rile
Acrolein
Can ID
Cone.
ppbv
139.85
73.75
0.29
2.14
101.63
< MQL
< MQL
101.84
6.08
0.87
1.45
< MQL
1.71
< MQL
56.95
< MQL
12.75
182.90
368
Page 11 of 26
Cone. Cone.
ppbv ppbv
107.06 83 .88
61.77 33.24
0.35 0.35
2.53 0.94
48.29 21.61
< MQL < MQL
< MQL < MQL
73.85 57.98
4.18 3.47
1.85 0.74
1.77 < MQL
< MQL < MQL
< MQL < MQL
< MQL < MQL
24.50 15.05
< MQL < MQL
13.98 3.72
97.20 57.61
700 744
ORD NH Report #4 September I 0, 2018
Location MS Tower MS Tower MS Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/27/2018 4/27/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
Acetone >413.776 >404.709 >410.84
iso-Pentane 17.77 41.61 8.88
Tri ch Io rofl u o ro methane < MQL < MQL < MQL
lsopropyl Alcohol 46.78 36.05 35.94
1-Pentene 2.32 1.42 0.82
Acrylonitrile 0.78 1.32 < MQL
n-Pentane 1.28 3.03 0.88
lsoprene 0.52 0.48 0.28
trans-2-pentene < MQL < MQL < MQL
cis-2-pentene < MQL < MQL < MQL
Tert-Butanol 1.54 1.04 < MQL
1,1-Dichloroethene < MQL < MQL < MQL
Methylene Chloride <MQL < MQL < MQL
3-Chloro-1-Propene < MQL < MQL < MQL
1, 1,2-T rich loro-1, 2, 2-trifluo roetha ne < MQL < MQL < MQL
Carbon Disulfide 1.43 1.10 0.82
2,2-Dimethylbutane < MQL < MQL < MQL
trans-1,2-Dich loroethene < MQL < MQL < MQL
Cyclopentane 16.87 10.25 < MQL
2,3-Dimethylbutane < MQL < MQL < MQL
1,1-Dichloroethane < MQL < MQL < MQL
Methyl-t-Butyl-Ether < MQL < MQL < MQL
Vinyl Acetate 45.72 34.31 26.88
2-Methylpentane < MQL < MQL < MQL
2-Butanone 150.61 53.48 43 .89
3-Methylpentane 0.61 0.91 < MQL
2-Chloroprene < MQL < MQL < MQL
1-Hexene 2.05 1.21 0.40
cis-1,2-Dichloroethene < MQL < MQL < MQL
Diisopropyl ether < MQL < MQL < MQL
Ethyl Acetate <MQL < MQL < MQL
n-Hexane < MQL 0.66 < MQL
Chloroform < MQL < MQL < MQL
Tetrahydrofuran 3.37 3.74 2.48
Ethyl Tert-Butyl Ether < MQL < MQL < MQL
Methylcyclopentane < MQL 0.23 < MQL
Can ID 368 700 744
Page 12 of26
ORD NH Report #4 September I 0, 20 18
Location MS Tower MS Tower MS Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/27/2018 4/27/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
1,2-Dichloroethane < MQL < MQL < MQL
2,4-Dimethylpentane 0.74 0.43 0.23
1,1,1-Trichloroethane < MQL < MQL < MQL
Benzene 110.06 21.07 5.21
Carbon Tetrachloride < MQL < MQL < MQL
Cyclohexane 0.81 1.53 0.64
2-Methylhexane 0.50 1.36 < MQL
2,3-Dimethylpentane < MQL < MQL < MQL
Tert Amyl Methyl Ether < MQL < MQL < MQL
3-methylhexane 3.38 1.56 < MQL
1,2-Dichloropropane < MQL < MQL < MQL
Bromodichloromethane < MQL < MQL < MQL
1,4-Dioxane 16.22 10.98 < MQL
Trichloroethene <MQL < MQL < MQL
lsooctane < MQL < MQL < MQL
Methyl Methacrylate < MQL < MQL < MQL
Heptane < MQL 1.59 < MQL
cis-1,3-Dichloropropene < MQL < MQL < MQL
4-Methy-2-Pentanone 204.92 121.73 102.23
Methylcyclohexane 0.38 1.30 < MQL
tra ns-1,3-Dichloropropene < MQL < MQL < MQL
1, 1,2-Trich lo roetha ne <MQL < MQL < MQL
2,3,4-Trimethylpentane < MQL 0.26 < MQL
Toluene 21.40 49.50 4.59
2-Methylheptane < MQL 0.52 < MQL
Dibromochloromethane <MQL < MQL < MQL
3-Methylheptane <MQL 1.93 1.02
1,2-Dibromoethane < MQL < MQL < MQL
Octane < MQL 0.62 < MQL
Tetrachloroethene <MQL < MQL < MQL
1,1,1,2-Tetrachloroethane < MQL < MQL < MQL
Chlorobenzene < MQL < MQL < MQL
Ethyl benzene 0.45 0.58 < MQL
m-Xylene <MQL 0.81 < MQL
p-Xylene < MQL < MQL < MQL
Bromoform < MQL < MQL < MQL
Can ID 368 700 744
Page 13 of 26
ORD NH Report #4 September I 0, 2018
Location MS Tower MS Tower MS Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/27/2018 4/27/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
Styrene < MQL < MQL < MQL
1,1,2,2-Tetrachloroethane < MQL < MQL < MQL
o-Xylene < MQL < MQL < MQL
Nonane 1.55 1.31 < MQL
Cumene < MQL 0.20 < MQL
n-Propylbenzene < MQL 0.37 < MQL
m-Ethyltoluene < MQL 0.41 < MQL
1,3,5-Trimethylbenzene < MQL < MQL < MQL
1,2,4-Trimethylbenzene < MQL < MQL < MQL
Tert-Butyl Benzene <MQL < MQL < MQL
1-Ethyl-4-Methyl Benzene < MQL < MQL < MQL
o-Ethyltoluene < MQL < MQL < MQL
1,3-Dichlorobenzene < MQL < MQL < MQL
1,4-Dichlorobenzene < MQL < MQL < MQL
n-Decane < MQL < MQL < MQL
Sec-Butyl Benzene < MQL < MQL < MQL
1,2,3-Trimethylbenzene < MQL < MQL < MQL
1,2-Dichlorobenzene < MQL < MQL < MQL
o-Cymene < MQL < MQL < MQL
1,3-Diethylbenzene < MQL 0.34 < MQL
1,2-Diethylbenzene < MQL 0.39 < MQL
n-Butyl Benzene < MQL < MQL < MQL
Undecane 0.90 1.28 < MQL
1,2,4-Trichlorobenzene < MQL < MQL < MQL
Naphthalene 0.80 0.63 < MQL
Dodecane 36.39 6.67 30.64
Hexachlorobutadiene <MQL < MQL < MQL
Page 14 of 26
ORD NH Report #4 September I 0, 20 18
Table 5. Measured concentrations of TO- 15 (plus PAMS) compounds in MA Tower SUMMA canisters.
MA Tower
Can ID
Location
Run Number
Date
Data Descriptors
• Contamination present. Quantitation suspect.
• Compound coelution problem. Quantitation not reliable.
• Above calibration range. Estimated value based on highest calibration point.
• Compounds below 3 x MDL are reported as '< MQL'
• Reported values are blank co rrected
Target Compounds
Propylene
Propane
Dichlorodifluoromethane
Chloromethane
lsobutane
D ich lo rotetrafluo roetha ne
Vinyl Chloride
1-Butene
1,3-Butadiene
Butane
trans-2-butene
Bromomethane
cis-2-butene
Chloroethane
Ethanol
Vinyl Bromide
Aceton itrile
Acrolein
Can ID
755
MA Tower
Run 1
4/26/2018
Cone.
ppbv
785.39
42.35
< MQL
0.55
63 .97
< MQL
< MQL
>422.306
22.46
< MQL
1.99
< MQL
< MQL
< MQL
52.08
< MQL
11.25
>432.824
755
Page 15 of 26
751 262
MA Tower MA Tower
Run2 Run3
4/26/2018 4/26/2018
Cone. Cone.
ppbv ppbv
807.99 713 .21
45.75 72.05
0.30 0.29
0.78 1.01
77.06 77.51
< MQL < MQL
< MQL < MQL
>425.27 >382.704
24.92 24.15
1.35 1.61
5.72 4.54
< MQL < MQL
1.47 3.49
<MQL < MQL
60.82 57.70
< MQL < MQL
16.80 14.67
>435.861 >392.235
751 262
ORD NH Report #4 September I 0, 2018
Location MA Tower MA Tower MA Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/26/2018 4/26/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
Acetone >436.869 >439.935 >395.901
iso-Pentane 5.22 173.42 179.83
Trichlorofluoromethane < MQL < MQL < MQL
lsopropyl Alcohol 101.44 110.01 117.79
1-Pentene 2.37 1.11 1.70
Acrylonitrile 9.03 7.73 7.23
n-Pentane < MQL 0.91 1.05
lsoprene 3.61 3.81 3.35
tra ns-2-pentene 0.56 0.74 0.68
cis-2-pentene 0.40 0.41 0.39
Tert-Butanol 4.18 3.34 2.87
1, 1-Dichloroethene < MQL < MQL < MQL
Methylene Chlo ride < MQL < MQL < MQL
3-Chloro-1-Propene < MQL 0.68 0.55
1, 1, 2-Trich loro-1,2,2-trifl uoroet ha ne < MQL < MQL < MQL
Carbon Disulfide < MQL < MQL < MQL
2,2-Dimethylbutane < MQL < MQL < MQL
tra ns-1, 2-D ich loroethen e < MQL < MQL < MQL
Cyclo pe nta ne 7.37 4.06 1.87
2,3-Dimethylbutane 1.53 < MQL < MQL
1,1-Dichloroethane < MQL < MQL < MQL
M ethyl-t -Butyl-Ether < MQL <MQL < MQL
Vinyl Acetate 86.92 74.80 74.27
2-Methylpentane 1.51 < MQL < MQL
2-Butanone 203 .94 172.34 151.31
3-Methylpentane 1.71 1.66 0.88
2-Chloroprene < MQL 0.17 0.09
1-Hexene 5.70 5.86 5.67
cis-1,2-D ich loroethene < MQL < MQL < MQL
Di isopropyl ether 0.57 0.29 0.45
Ethyl Acetate < MQL < MQL < MQL
n-Hexane 0.97 0.87 0.43
Chloroform < MQL < MQL 0.11
Tetra hyd rofu ran 15.84 16.94 15.40
Ethyl Tert-Butyl Ether < MQL < MQL < MQL
Methylcyclopentane < MQL < MQL < MQL
1,2-Dichloroethane < MQL < MQL < MQL
2,4-Dimethylpentane 1.89 2.61 2.65
Can ID 755 751 262
Page 16 of26
ORD N H Report #4 September I 0, 20 18
Location MA Tower MA Tower MA Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/26/2018 4/26/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
1, 1, 1-Trichloroethane < MQL < MQL < MQL
Benzene 11.52 11.08 9.88
Carbon Tetrachloride < MQL < MQL < MQL
Cyclohexane < MQL 1.55 1.28
2-Methylhexane 5.15 0.91 1.87
2,3-Dimethylpentane 0.84 < MQL < MQL
Tert Amyl Methyl Ether < MQL < MQL < MQL
3-methylhexane 5.93 4.07 4.41
1,2-Dichloropropane < MQL < MQL < MQL
Bromodichloromethane < MQL < MQL < MQL
1,4-Dioxane 18.91 21.63 17.61
Trichloroethene < MQL < MQL < MQL
lsooctane < MQL 0.57 < MQL
Methyl Methacrylate < MQL < MQL < MQL
Heptane 5.67 < MQL < MQL
cis-1,3-D ich lo roprope ne < MQL < MQL < MQL
4-Methy-2-Pentanone >420.217 >423.166 >380.811
Methylcyclohexane 1.93 1.66 0.86
trans-1,3-Dichloropropene < MQL < MQL < MQL
1,1,2-Trichloroethane < MQL < MQL < MQL
2,3,4-Trimethylpentane < MQL 0.99 0.70
Toluene 57.88 73 .57 14.32
2-Methylheptane 0.76 0.88 < MQL
Dibromochloromethane < MQL < MQL < MQL
3-Methylheptane 1.54 < MQL 0.93
1,2-Dibromoethane < MQL < MQL < MQL
Octane 1.00 1.99 0.63
Tetrachloroethene < MQL < MQL < MQL
1, 1, 1,2-Tetrachloroetha ne < MQL < MQL < MQL
Chlorobenzene < MQL < MQL < MQL
Ethyl benzene < MQL 0.45 < MQL
m-Xylene 1.42 2.96 1.58
p-Xylene < MQL 1.00 < MQL
Bromoform < MQL < MQL < MQL
Styrene < MQL < MQL < MQL
1, 1,2,2-Tetrachloroethane < MQL 0.75 < MQL
o-Xylene < MQL < MQL < MQL
Nonane 3.77 5.58 5.01
Can ID 755 751 262
Page 17 of 26
0 RD NH Report #4 September I 0, 2018
Location MA Tower MA Tower MA Tower
Run Number Run 1 Run 2 Run 3
Date 4/26/2018 4/26/2018 4/26/2018
Target Compounds Cone. Cone. Cone.
ppbv ppbv ppbv
Cumene < MQL 0.24 0.24
n-Propylbenzene <MQL 0.52 0.50
m-Ethyltoluene < MQL 0.67 0.56
1,3,5-Trimethylbenzene <MQL 0.64 0.70
1,2,4-Trimethylbenzene <MQL < MQL < MQL
Tert-Butyl Benzene < MQL < MQL < MQL
1-Ethyl-4-Methyl Benzene < MQL < MQL < MQL
o-Ethyltoluene < MQL < MQL < MQL
1,3-Dichlorobenzene < MQL < MQL < MQL
1,4-Dichlorobenzene < MQL < MQL < MQL
n-Decane < MQL 0.58 0.39
Sec-Butyl Benzene < MQL < MQL < MQL
1,2,3-Trimethylbenzene < MQL < MQL < MQL
1,2-Dichlorobenzene < MQL < MQL < MQL
o-Cymene < MQL < MQL < MQL
1,3-Diethylbenzene < MQL 0.51 0.41
1,2-Diethylbenzene < MQL 0.92 0.68
n-Butyl Benzene < MQL < MQL < MQL
Undecane 1.60 2.47 1.86
1,2,4-Trichlorobenzene < MQL < MQL < MQL
Naphthalene 0.88 0.86 0.60
Dodecane 33.32 >394.967 >355.434
Hexachlorobutadiene < MQL < MQL < MQL
Page 18 of 26
ORD NH Report #4 September I 0, 20 18
Table 6. Measured concentrations of T0-1 5 (plus PAMS) compounds in QX tower Inlet and Outlet SUMMA canisters.
QX Tower Inlet
Can ID
Location
Run Number
Date
Data Descriptors
• Contamination present. Quantitation suspect.
• Compound coelution problem. Quantitation not reliable.
• Above calibration range. Estimated value based on highest calibration point.
• Compounds below 3 x MDL are reported as '< MQL'
• Reported values are blank corrected
Target Compounds
Propylene
Propane
Dichlorodifluoromethane
Chloromethane
lsobutane
Dichlorotetrafluoroethane
Vinyl Chloride
1-Butene
1,3-Butadiene
Butane
trans-2-butene
Bromomethane
cis-2-butene
Chloroethane
Ethanol
Vinyl Bromide
Aceton itrile
721 176
QX Inlet QX Inlet
Run 1 Run 2
4/30/2018 5/1/2018
Cone. Cone.
ppbv ppbv
83.76 82.14
51.55 55.36
0.28 0.31
2.74 2.41
94.75 91.61
< MQL < MQL
< MQL < MQL
56.85 53 .77
3.01 4.41
1.57 2.54
6.86 6.33
< MQL < MQL
3.54 2.73
< MQL < MQL
106.39 66.12
< MQL < MQL
1.64 2.26
Page 19 of 26
QX Tower Outlet
a378 321 2045 793
QX In let QX Outlet QX Outlet QX Outlet
Run 3 Run 1 Run 2 Run 3
5/1/2018 4/30/2018 5/1/2018 5/1/2018
Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv
25.62 72.09 76.45 20.43
33.08 45 .49 50.09 25.20
0.39 0.29 0.32 0.30
0.51 2.74 3.93 0.43
12.21 109.26 44.87 13.30
< MQL <MQL < MQL < MQL
< MQL <MQL < MQL < MQL
21.66 50.36 62.84 20.08
<MQL 2.83 4.22 < MQL
2.74 1.54 2.23 1.57
<MQL 5.94 6.64 < MQL
< MQL < MQL < MQL < MQL
<MQL 2.55 2.82 < MQL
< MQL < MQL < MQL < MQL
18.04 75.57 58.78 16.64
<MQL < MQL < MQL < MQL
< MQL 2.34 7.85 < MQL
ORD NH Report #4 September I 0, 20 18
Can ID 721 176 a378 321 2045 793
Location QX Inlet QX Inlet QX Inlet QX Outlet QX Outlet QX Outlet
Run Number Run 1 Run 2 Run 3 Run 1 Run 2 Run 3
Date 4/30/2018 5/1/2018 5/1/2018 4/30/2018 5/1/2018 5/1/2018
Target Compounds Cone. Cone. Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv ppbv ppbv
Acrolein 169.37 149.40 22.33 143.40 161.90 25.00
Acetone >442.145 >402.705 101.48 >389.992 >384.943 83.10
iso-Pentane 5.15 18.76 6.72 20.11 6.69 1.79
Trichlorofluoromethane < MQL < MQL < MQL <MQL < MQL < MQL
lsopropyl Alcohol 64.49 52.81 31.16 35.41 40.06 19.38
1-Pentene 1.08 1.61 0.96 1.97 1.44 < MQL
Acrylonitrile 5.96 <MQL 0.72 5.14 < MQL < MQL
n-Pentane 0.26 0.72 1.32 0.35 0.31 < MQL
lsoprene 2.03 1.89 0.66 2.04 2.29 < MQL
trans-2-pentene 1.58 1.52 0.69 1.25 1.43 < MQL
cis-2-pentene 2.05 1.78 0.66 1.40 1.26 < MQL
Tert-Butanol 23 .59 20.72 1.00 12.03 13.35 0.61
1, 1-Dichloroethene < MQL < MQL < MQL <MQL < MQL <MQL
Methylene Chloride < MQL < MQL <MQL <MQL < MQL < MQL
3-Chloro-1-Propene < MQL < MQL < MQL <MQL < MQL < MQL
1, 1,2-Trich loro-1,2,2-trifluoroethane < MQL < MQL < MQL <MQL < MQL < MQL
Carbon Disulfide < MQL < MQL < MQL 0.53 0.84 < MQL
2,2-Dimethylbutane <MQL <MQL 0.70 <MQL < MQL < MQL
tra ns-1,2-Dichloroethene < MQL < MQL <MQL <MQL <MQL < MQL
Cyclopentane < MQL < MQL 0.77 1.68 30.29 < MQL
2,3-Dimethylbutane < MQL < MQL 0.57 <MQL < MQL < MQL
1, 1-Dichloroetha ne < MQL < MQL < MQL < MQL < MQL <MQL
M ethyl-t-Butyl-Ether <MQL <MQL <MQL <MQL < MQL < MQL
Vinyl Acetate 43.93 41.08 3.13 48.62 39.36 3.24
2-Methylpentane < MQL <MQL 1.10 <MQL < MQL < MQL
2-Butanone 140.46 138.84 11.78 121.79 157.59 8.05
3-Methylpentane 16.02 16.07 1.57 12.65 14.44 0.35
2-Chloroprene < MQL 0.71 0.16 <MQL < MQL < MQL
1-Hexene 4.30 3.93 0.89 3.92 4.52 < MQL
cis-1,2-Dichloroethene < MQL < MQL < MQL <MQL < MQL < MQL
Diisopropyl ether 0.27 <MQL <MQL 0.28 < MQL < MQL
Ethyl Acetate < MQL < MQL < MQL < MQL < MQL < MQL
n-Hexane < MQL 0.52 0.85 0.32 0.39 < MQL
Chloroform <MQL < MQL < MQL < MQL < MQL < MQL
Tetrahydrofuran 1.09 1.73 2.82 < MQL < MQL 1.93
Ethyl Tert-Butyl Ether < MQL < MQL < MQL <MQL < MQL < MQL
Methylcyclopentane < MQL 0.33 0.90 0.40 0.28 < MQL
1,2-Dichloroethane < MQL < MQL < MQL <MQL < MQL < MQL
Page 20 of26
ORD NH Report #4 September 10, 2018
Can ID 721 176 a378 321 2045 793
Location QX Inlet QX Inlet QX Inlet QX Outlet QX Outlet QX Outlet
Run Number Run 1 Run 2 Run 3 Run 1 Run 2 Run 3
Date 4/30/2018 5/1/2018 5/1/2018 4/30/2018 5/1/2018 5/1/2018
Target Compounds Cone. Cone. Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv ppbv ppbv
2,4-Dimethylpentane 0.53 0.68 1.71 0.45 0.49 0.65
1, 1,1-Trichloroethane < MQL < MQL < MQL < MQL < MQL < MQL
Benzene 0.98 1.06 1.05 2.19 2.20 < MQL
Carbon Tetrachloride < MQL < MQL < MQL < MQL < MQL < MQL
Cyclohexane 2.15 0.38 1.29 1.67 0.93 0.41
2-Methylhexane 0.77 2.40 1.23 2.03 0.38 <MQL
2,3-Dimethylpentane < MQL < MQL 0.64 < MQL < MQL <MQL
Tert Amyl Methyl Ether < MQL < MQL < MQL < MQL < MQL < MQL
3-methylhexane 0.94 1.34 0.92 < MQL < MQL 0.50
1,2-Dichloropropane < MQL < MQL < MQL < MQL < MQL < MQL
Bromodichloromethane < MQL < MQL < MQL <MQL < MQL < MQL
1,4-Dioxane 51.40 41.04 19.07 37.80 35.69 17.12
Trichloroethene < MQL < MQL < MQL <MQL < MQL < MQL
lsooctane 2.72 2.55 1.06 2.40 2.51 0.34
Methyl Methacrylate <MQL < MQL < MQL < MQL < MQL < MQL
Heptane 3.93 4.16 1.12 3.48 4.04 < MQL
cis-1,3-Dichloropropene < MQL < MQL < MQL < MQL < MQL < MQL
4-Methy-2-Pentanone 38.54 34.44 45.11 42.78 44.52 36.41
Methylcyclohexane 0.61 0.65 1.10 0.65 0.62 0.64
trans-1,3-Dichloropropene < MQL <MQL <MQL <MQL < MQL < MQL
1, 1,2-Trichloroethane < MQL < MQL < MQL < MQL < MQL < MQL
2,3,4-Trimethylpentane < MQL < MQL < MQL <MQL < MQL < MQL
Toluene 9.41 10.11 5.77 8.31 9.57 4.63
2-Methylheptane 18.88 18.26 1.01 14.02 14.73 < MQL
Dibromochloromethane < MQL < MQL < MQL <MQL < MQL <MQL
3-Methylheptane <MQL 6.36 < MQL 1.88 2.48 < MQL
1,2-Dibromoethane < MQL < MQL < MQL < MQL < MQL < MQL
Octane < MQL 0.85 0.81 <MQL < MQL < MQL
Tetrachloroethene < MQL < MQL < MQL < MQL < MQL < MQL
1, 1, 1,2-Tetrachloroethane < MQL < MQL < MQL < MQL < MQL < MQL
Chlorobenzene <MQL <MQL <MQL < MQL < MQL < MQL
Ethyl benzene <MQL < MQL 0.65 < MQL < MQL < MQL
m-Xylene < MQL < MQL < MQL < MQL < MQL < MQL
p-Xylene <MQL < MQL <MQL < MQL < MQL < MQL
Bromoform < MQL < MQL 0.18 < MQL < MQL < MQL
Styrene < MQL <MQL <MQL < MQL < MQL < MQL
1,1,2,2-Tetrachloroethane < MQL < MQL < MQL < MQL < MQL < MQL
a-Xylene < MQL < MQL < MQL < MQL < MQL < MQL
Page 21 of 26
ORD NH Report #4 September I 0, 20 18
Can ID 721 176 a378 321 2045 793
Location QX Inlet QX Inlet QX Inlet QX Outlet QX Outlet QX Outlet
Run Number Run 1 Run 2 Run 3 Run 1 Run 2 Run 3
Date 4/30/2018 5/1/2018 5/1/2018 4/30/2018 5/1/2018 5/1/2018
Target Compounds Cone. Cone. Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv ppbv ppbv
Nonane 0.87 0.98 0.82 0.82 0.89 < MQL
Cumene < MQL 0.20 0.70 0.20 0.22 <MQL
n-Propylbenzene <MQL 0.47 0.63 0.38 0.38 < MQL
m-Ethyltoluene < MQL 0.51 0.47 0.48 0.54 < MQL
1,3,5-Trimethylbenzene < MQL < MQL 0.55 < MQL < MQL < MQL
1,2,4-Trimethylbenzene < MQL < MQL < MQL <MQL < MQL <MQL
Tert-Butyl Benzene < MQL < MQL < MQL < MQL < MQL <MQL
1-Ethyl-4-Methyl Benzene < MQL < MQL < MQL < MQL < MQL < MQL
o-Ethyltoluene < MQL < MQL < MQL < MQL < MQL < MQL
1,3-Dichlorobenzene < MQL < MQL < MQL < MQL < MQL <MQL
1,4-Dichlorobenzene < MQL < MQL < MQL < MQL < MQL < MQL
n-Decane <MQL < MQL 0.50 0.50 < MQL < MQL
Sec-Butyl Benzene < MQL < MQL < MQL <MQL < MQL <MQL
1,2,3-Trimethylbenzene < MQL 0.41 0.45 0.39 < MQL < MQL
1,2-Dichlorobenzene <MQL < MQL < MQL < MQL < MQL < MQL
o-Cymene < MQL < MQL < MQL <MQL < MQL <MQL
1,3-Diethylbenzene < MQL 0.40 0.57 0.38 0.38 < MQL
1,2-Diethylbenzene <MQL 0.40 0.61 0.51 0.46 <MQL
n-Butyl Benzene < MQL < MQL < MQL <MQL < MQL <MQL
Undecane 1.73 2.68 1.47 2.47 2.27 < MQL
1,2,4-Trichlorobenzene < MQL < MQL 0.60 < MQL 0.73 <MQL
Naphthalene < MQL <MQL < MQL 0.58 0.90 <MQL
Dodecane 2.62 34.92 1.55 9.73 42.10 38.70
Hexachlorobutadiene <MQL < MQL < MQL < MQL < MQL < MQL
Page 22 of26
ORD NH Report #4 September I 0, 20 18
Table 7. Measured concentrations of T0-15 (plus PAMS) compounds in ambient samples and a single field blank.
Ambient
Can ID
Sample Type
Location
Date
Data Descriptors
• Contamination present. Quantitation suspect.
• Compound coelution problem. Quantitation not reliable.
• Above calibrat ion range. Estimated value based on highest calibration point.
• Compounds below 3 x MDL are reported as'< MQL'
• Reported values are blank corrected
Target Compounds
Propylene
Propane
Dichlorodifluoromethane
Chloromethane
lsobutane
D ich lo rotetrafluoroetha ne
Vinyl Chloride
1-Butene
1,3-Butadiene
Butane
trans-2-butene
Bromomethane
cis-2-butene
Chloroethane
Ethanol
Vinyl Bromide
Acetonitrile
005
Ambient
(lower roof)
5/1/2018
Cone.
ppbv
0.46
1.49
0.34
0.53
0.88
<MQL
< MQL
< MQL
< MQL
0.60
< MQL
< MQL
< MQL
< MQL
2.70
< MQL
< MQL
794
Ambient
(upper roof)
4/27/2018
Cone.
ppbv
< MQL
2.40
0.31
< MQL
< MQL
< MQL
< MQL
<MQL
< MQL
< MQL
< MQL
< MQL
< MQL
< MQL
5.43
< MQL
< MQL
Page 23 of26
rk9
Ambient
(inside fac.)
5/1/2018
Cone.
ppbv
2.30
10.04
0.32
0.55
1.48
< MQL
< MQL
< MQL
< MQL
0.60
< MQL
< MQL
< MQL
< MQL
14.92
< MQL
0.48
Field Blank
709
Field Blank
4/30/2018
Cone.
ppbv
0.14
0.30
< MQL
< MQL
< MQL
< MQL
< MQL
<MQL
< MQL
< MQL
< MQL
< MQL
< MQL
< MQL
< MQL
< MQL
< MQL
ORD NH Report #4 September I 0, 20 18
Can ID 005 794 rk9 709
Sample Type Ambient Ambient Ambient Field Blank
Location (lower roof) (upper roof) (inside fac.)
Date 5/1/2018 4/27/2018 5/1/2018 4/30/2018
Target Compounds Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv
Acrolein 0.77 < MQL 1.74 0.12
Acetone 5.83 < MQL 6.50 < MQL
iso-Pentane 0.82 < MQL 0.66 < MQL
Trichlorofluoromethane < MQL < MQL 0.21 < MQL
lsopropyl Alcohol 5.57 3.10 9.80 < MQL
1-Pentene < MQL < MQL < MQL < MQL
Acrylonitrile 1.19 < MQL < MQL < MQL
n-Pentane 15.14 < MQL 0.13 < MQL
lsoprene <MQL < MQL 0.57 < MQL
trans-2-pentene < MQL < MQL < MQL < MQL
cis-2-pentene < MQL < MQL < MQL < MQL
Tert-Butanol < MQL < MQL 0.15 < MQL
1, 1-Dichloroethene < MQL < MQL < MQL < MQL
Methylene Chloride <MQL < MQL < MQL < MQL
3-Chloro-1-Propene < MQL < MQL < MQL < MQL
1, 1,2-Trichloro-1,2,2-trifluoroethane < MQL < MQL < MQL < MQL
Carbon Disulfide < MQL < MQL < MQL < MQL
2,2-Dimethylbutane < MQL < MQL < MQL < MQL
tra ns-1,2-D ich loroethe ne <MQL < MQL < MQL < MQL
Cyclopentane < MQL < MQL < MQL < MQL
2,3-Dimethylbutane < MQL < MQL < MQL < MQL
1,1-Dichloroethane < MQL < MQL < MQL < MQL
Methyl-t-Butyl-Ether < MQL < MQL < MQL < MQL
Vinyl Acetate < MQL < MQL 0.73 < MQL
2-Methylpentane < MQL < MQL <MQL < MQL
2-Butanone < MQL < MQL 18.27 < MQL
3-Methylpentane < MQL < MQL 0.38 < MQL
2-Chloroprene < MQL < MQL < MQL < MQL
1-Hexene < MQL < MQL < MQL < MQL
cis-1,2-Dichloroethene < MQL < MQL < MQL < MQL
Diisopropyl ether < MQL < MQL < MQL < MQL
Ethyl Acetate < MQL < MQL <MQL < MQL
n-Hexane < MQL < MQL 0.36 < MQL
Chloroform < MQL < MQL < MQL < MQL
Tetrahydrofuran < MQL < MQL < MQL < MQL
Ethyl Tert-Butyl Ether < MQL < MQL < MQL < MQL
M ethylcyclopenta ne < MQL < MQL 0.15 < MQL
1,2-Dichloroethane < MQL < MQL < MQL < MQL
Page 24 of 26
ORD NH Report #4 September I 0, 2018
Can ID 005 794 rk9 709
Sample Type Ambient Ambient Ambient Field Blank
Location (lower roof) (upper roof) (inside fac.)
Date 5/1/2018 4/27/2018 5/1/2018 4/30/2018
Target Compounds Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv
2,4-Dimethylpentane < MQL < MQL 0.09 < MQL
1, 1,1-Trichloroethane < MQL < MQL < MQL < MQL
Benzene < MQL < MQL < MQL < MQL
Carbon Tetrachloride < MQL < MQL < MQL < MQL
Cyclohexane 0.25 < MQL 0.26 < MQL
2-Methylhexane < MQL < MQL 0.52 < MQL
2,3-Dimethylpentane < MQL < MQL < MQL < MQL
Tert Amyl Methyl Ether < MQL < MQL < MQL < MQL
3-methylhexane < MQL < MQL 0.63 < MQL
1,2-Dichloropropane < MQL < MQL < MQL < MQL
Bromodichloromethane < MQL < MQL < MQL < MQL
1,4-Dioxane < MQL <MQL < MQL < MQL
Trichloroethene < MQL < MQL < MQL < MQL
lsooctane < MQL < MQL < MQL < MQL
Methyl Methacrylate < MQL < MQL < MQL < MQL
Heptane < MQL < MQL 0.84 < MQL
cis-1,3-Dichloropropene < MQL < MQL <MQL < MQL
4-Methy-2-Pentanone < MQL < MQL < MQL < MQL
Methylcyclohexane < MQL <MQL 0.95 < MQL
tra ns-1,3-D ich lo ro pro pe ne < MQL < MQL < MQL < MQL
1, 1,2-Trichloroethane < MQL < MQL < MQL < MQL
2,3,4-Trimethylpenta ne < MQL < MQL < MQL < MQL
Toluene 1.22 < MQL 33 .75 < MQL
2-Methylheptane < MQL < MQL 0.25 < MQL
Dibromochloromethane < MQL < MQL <MQL < MQL
3-Methylheptane < MQL <MQL <MQL < MQL
1,2-Dibromoethane < MQL < MQL < MQL < MQL
Octane < MQL < MQL <MQL < MQL
Tetrachloroethene < MQL < MQL < MQL < MQL
1,1,1,2-Tetrachloroethane < MQL < MQL <MQL < MQL
Chlorobenzene < MQL < MQL < MQL < MQL
Ethylbenzene < MQL < MQL < MQL < MQL
m-Xylene < MQL < MQL <MQL < MQL
p-Xylene < MQL < MQL <MQL < MQL
Bromoform < MQL < MQL < MQL < MQL
Styrene < MQL < MQL < MQL < MQL
1,1,2,2-Tetrachloroethane < MQL < MQL < MQL < MQL
a-Xylene < MQL < MQL <MQL < MQL
Page 25 of26
ORD NH Report #4 September I 0, 2018
Can ID 005 794 rk9 709
Sample Type Ambient Ambient Ambient Field Blank
Location (lower roof) (upper roof) (inside fac.)
Date 5/1/2018 4/27/2018 5/1/2018 4/30/2018
Target Compounds Cone. Cone. Cone. Cone.
ppbv ppbv ppbv ppbv
Nonane < MQL < MQL < MQL <MQL
Cumene < MQL < MQL 0.08 < MQL
n-Propylbenzene < MQL < MQL < MQL < MQL
m-Ethyltoluene < MQL < MQL < MQL < MQL
1,3,5-Trimethylbenzene < MQL < MQL < MQL <MQL
1,2,4-Trimethylbenzene < MQL < MQL < MQL < MQL
Tert-Butyl Benzene < MQL < MQL < MQL < MQL
1-Ethyl-4-Methyl Benzene < MQL < MQL < MQL < MQL
o-Ethyltoluene < MQL < MQL < MQL < MQL
1,3-Dichlorobenzene < MQL < MQL < MQL < MQL
1,4-Dichlorobenzene < MQL < MQL < MQL < MQL
n-Decane < MQL < MQL < MQL <MQL
Sec-Butyl Benzene < MQL < MQL < MQL < MQL
1, 2,3-Trimethylbenzene < MQL < MQL < MQL < MQL
1,2-Dichlorobenzene < MQL <MQL < MQL < MQL
o-Cymene < MQL 0.54 < MQL < MQL
1,3-Diethylbenzene < MQL < MQL < MQL <MQL
1,2-Diethylbenzene < MQL < MQL < MQL < MQL
n-Butyl Benzene < MQL < MQL < MQL < MQL
Undecane 0.63 < MQL 0.73 < MQL
1,2,4-Trichlorobenzene < MQL < MQL < MQL < MQL
Naphthalene < MQL < MQL 0.35 < MQL
Dodecane 6.48 1.31 2.87 0.17
Hexachlorobutadiene < MQL < MQL < MQL <MQL
Page 26 of 26
